The Solid State G 5 a oes 5 Topic Name Sub-Topic ins, [LOD |Qns.|LOD ans. |LOD Qns.|LOD| )D | Spee Servant Bravais lattice rie of Solids | relation between rand a LIA Cubic system and 2/A 1[e alfa pring effteney, 9FTUla of compound and volds density ratio and structure 1[A 1|o i impetecion defects rfa in Solids —— 4. The ability of a substances to assume two or Topic-1: Properties and ‘Types of Solids more crystalline structures is called 1990 |. A solid with igh electrical and thermal hemes 0) Polya conductivity from the following is 1994 (©)_Isomorphism __(@)_Amorphism ; @) Si) Li (©) NaCl (d) Ice Topi rystal Structure of Solids + The pure crystalline substance on being heated gradually frst forms a turbid liquid at constant 5- The correct option for the number of body temperature and still at higher temperature centred unit cells in all 14 types of Bravais turbidity completely disappears. The behaviour lattice unit cells is NCERT | Page-10 |2021 isa characteristic of substance forming 1998, (a) 3 (b) 7 @ 5 @2 (4) Allotropic crystals 6, In calcium fluoride, having the fluorite (0) Liquid erystals structure, the coordination numbers for calcium ion (Ca?") and fluoride ion (F>) are (4 Isomorphous crystals NCERY | Page-18 | Ph-11 2016 Most crystals show good cleavage because (a) Sand4 (b) 4and8 ‘heir atoms, ions or molecules are (c) 4and2 (d@) 6and6 NCERE|Page2 [199 7. A solid compound XY has NaCl structure, If (©) Isomeric crystals i weakly bonded together i. Sa i a is 100 pm, the radius of ; Strongly bonded together 20M ©) spherically symmetrical (a) 275.1 pm (b) 322.5 pm (4) arranged in planes. (c) 241.5 pm (@) 165.7 pm ae12. ‘A compound formed by elements X and Y crystallizes in a cubic structure in which the X atoms are at the comers of a cube and the Y atoms are at the face-centres, The formula of the compound is j2o04 @ X% ©) x (©) x¥ @ XY, The pyknometric density of sodium chloride crystal is 2.165 = 103 kg mr while its X-ray density is 2.178 x 103 kg m™, The fraction of unoccupied sites in sodium chloride crystal is (a) 5.96 x 103 (b) 5.96 , (c) 5.96 x 107 @ 5.96 x 10"! When molten zinc is converted into solid state, it acquires hep structure. The number of nearest neighbours will be 01 @6 12 ©8& @4 A compound is formed by elements A and B. The crystalline cubic structure has the 4 atoms at the comers of the cube and B atoms at the body centre. The simplest formula of the compound is z 2000 (@) AB (b) AgB_ (©) AB, (A) AgBy In the solid state, MgO has the same structure as that of sodium chloride. The number of oxygens surrounding each magnesium in MgO is @6 1 ©2 @4 For orthorhombic system, axial ratios are ab #c and the axial angles are NCERD| Page-10| 1991 (@) a=B=y490° () a y= 90° () a 90°, B # 90° (@) azBey=90° Topie-g: Cubic System and Packing Efficiency What fraction of one edge centred octahedral void lies in one unit cell of fec? 1 1 1 1 @ z () O47 OF A compound is formed by two elements A and B. The element B forms cubic close packed structure and atoms of A occupy 1/3 of tetrahedral voids. If the formula of the 2023, 16. 17. 18. 19. 20. 21. Chemistry compound is A,B,, then the value of X+ yisin option NCERT | Page-18 2021 fa) 5 ) 4 © 3 @2 Copper crystallises in fec unit cell with cell edge length of 3.608 x 10-8 cm. The density of copper is 8.92 g om™. Calculate the atomic mass of copper. (NCERT | Page-22 | 20225 Similar 2013 (a) 31.550 (b) 60u (c) 65u @ 63.1u Right option for the number of tetrahedral and octahedral voids in hexagonal primitive unit cell are : NCERT] Page-16)17/2021 (a) 12,6 ©) 84 © 612@21 An element has a body centered cubic (bcc) structure with a cell edge of 288 pm. The atomic radius is: Neprr)Page21/200 v2 x 288 om (@) ~Px288pm —(&) 4 *288P 4 (© 7y%288rm —@ 4, 288pm A compound is formed by cation C and anion A, The anions form hexagonal close packed (hep) lattice and the cations occupy 75% of octahedral voids. The formula of the cor is: a (@) Cody (0) Cody (©) Coy @) Cs Iron exhibits bcc structure at room temperature Above 900°C, it transforms to fee structure The ratio of density of iron at room temperature to that at 900°C (assuming molar mass ad atomic radii of iron remains constant with temperature) is att 3 wa OR © 32 ) ; @ 4 42 Structure of a mixed oxide is cubic clos® packed (c.c,p), The cubic unit cell of mix! oxide is composed of oxide ions. One fourth of the tetrahedral voids are occupied by divale™ metal 4 and the octahedral voids are occup by a monovalent metal B, The formula of ti* oxide is : aoa (a) ABO, (b) 4,B0, (©) 4,80, (@) 4B,0, —_—lass-XII/Chapter-1/The Solid State 26. 29, The number of octahedral void(s) per atom present in a cubic close-packed structure is : NCERT | Page-17 |2012 (b) 3 @ 1 @ 2 @4 23, Ametal crystallizes with a face-centered cubic lattice. The edge length of the unit cell is 408 pm. The diameter of the metal atom is: 2012 (a) 288 pm (b) 408 pm () 14pm (204 pm AB crystallizes in a body centred cubic lattice with edge length ‘a’ equal to 387 pm. The distance between two oppositely charged ions in the lattice is : 2010M (a) 335 pm (b) 250 pm (c) 200pm (a) 300 pm . Copper crystallises in a face-centred cubic lattice with a unit cell length of 361 pm. What is the radius of copper atom in pm? 2009 (a) 157 (b) 181 (ce) 108 (a) 128 Lithium metal crystallises in a body centred cubic crystal. If the length of the side of the unit cell of lithium is 351 pm, the atomic radius of the lithium will be: 2009 (@) 151.8pm (b) 75.5 pm (©) 300.5 pm (@)_ 240.8 pm . Percentage of free space in a body centred cubic unit cell is : 2008 (@) 30% (b) 32% (©) 34% (@) 28% If ‘a’ stands for the edge length of the cubic systems: simple cubic, body centred cubic and face centred cubic, then the ratio of radii ofthe spheres in these systems will be respectively, NCERT | Page-20, 21 | 2008 @ 14.3, 1 1 Satta sa: y3a: gata 2 Rh © i 4 By (@) a:V3a:V2a 2 The fraction of total volume occupied by the atoms present in a simple cube is NCERT| Page-21 | 2007 © = — wi © Ms = z ” 4 @ 6 30. 31. 32. 33. 34. 35. 36. CsBr crystallises in a body centered cubic lattice. The unit cell length is 436.6 pm. Given that the atomic mass of Cs = 133 and that of Br = 80 amu and Avogadro number being 6.02 x 103 mol"! the density of CsBr is 2006 (a) 0.425 glem? = (b)_ 8.25 g/cm? (©) 4.25 g/cm? (a) 42.5 gem? In face-centred cubic lattice, a unit cell is shared equally by how many unit cells? NCERT | Page-13 | 2005 @ 2 (b) 4 @ 6 @s The second order Bragg diffraction of X-rays with 2 = 1.00 A from a set of parallel planes in a metal occurs at an angle 60°. The distance between the scattering planes in the crystal is 1998 (@) 0.575 (b) 1.00A (©) 2.004 @ LISA The intermetallic compound LiAg crystallizes in a cubic lattice in which’ both lithium and silver atoms have coordination number of eight, To what crystal class does the unit cell belong ? 1997 (a) Simple cubic (b) Face-centred cubic (©) Body-centred cubic (@)_ None The edge length of a face centred unit cubic cell is 508 pm. If the radius of the cation is 100 pm, the radius of the anion is 1996 (a) 288 pm (b) 398 pm (©) 154 pm (4) 618 pm In the fluorite structure, the coordination number of Ca** ion is : 1993 (a) 4 (b) 6 © 8 @3 The number of atoms contained in an fee unit cell of a monoatomic substance is NCERT| Page-13 | 1993 (b) 2 © 4 @e (a) |-4: Imperfection in Solids Topi 37. Match List - I with List - IT : 38. 39. NCERT | Page-24 25 & 26 JRS 2022 List -1 List - II (Defects) (shown by) (A) Frenkel defect (i) non-ionic solids and density of the solid decreases (B) Schottky defect (ii) non-ionic solids and density of the solid increases (C) Vacancy defect (iii) ionic solids and density of the solid decreases ionic solids and density of the solid remains constant Choose the correct answer from the options given below : (a) (A) - Gv), (B) - Gili), (© - @, D) - Gi) (b)_ (A) - @, (B) - Gi), (©) - (iii), (D) - (iv) (©) (A)- (i, B)- Git), (© - Gi), (D) - (iv) (a) (A)- (iv), (B) - (iii), (C) - Gi), D) - Given below are two statements: one is labelled as Assertion (A) and the other is labelled as Reason (R). Assertion (A): In a particular point defect, an ionic solid is electrically neutral, even if few of its cations are missing from its unit cells. Reason (R): In an ionic solid, Frenkel defect arises due to dislocation of cation from its lattice site to interstitial site, maintaining overall electrical neutrality, In the light of the above statements, choose the most appropriate answer from the options given below: NOERT | Page-25 [2022 (a) Both (A) and (R) are correct but (R) is not the correct explanation of (A). (b) (A) is correct but (R) is not correct, (c) (A) is not correct but (R) is correct. (d) Both (A) and (R) are correct and (R) is the correct explanation of (A). Formula of nickel oxide with metal deficiency defect in its crystal is Nig 90. The crystal contains Ni?* and Ni** ions. The fraction of nickel existing as Ni2* ions in the crystal is Odisha 2019 (D) Interstitial defect (iv) 40. 41. 42. 43. 44, 45. 46. Te Chemistry (a) 0.31 (b) 0.96 (c) 0.04 (@ 0.50 Which one of the following compounds shows both, Frenkel as well as Schottky defects? NCERT | Page25| Phatranig (a) ZnS (0) AgBr (© Agl (@_ Nac With which one of the following elements silicon should be doped so as to give p-type semiconductor ? ‘NCERT | Page-28 2008 (@) Germanium (b) Arsenic (©) Selenium @ Boron I£NaClis doped with 10-4 mol % of SrCl,the concentration of cation vacancies will be (N4 = 6.02 « 103 mot!) (a) 6.02 x 10!6 mot (b) 6.02 107 mol"! (©) 6.02 « 10!4 mot! (a) 6.02 x 10!5 mot The appearance of colour in solid alkali metal halides is generally due to (a) Schottky defect (b) Frenkel defect (©) Interstitial positions (d) F-centres Schottky defect in crystals is observed when INCERT | Page25 1199 an ion leaves its normal site and occupies an interstitial site (b) unequal number of cations and anions ate missing from the lattice (©) density of the crystal is increased (@ equal number of cations and anions 4 missing from the lattice ‘When electrons are trapped into the crystal it anion vacancy, the defect is known as NERF | Page251! wn @ (a) Schottky defect (b), Frenkel defect (©) Stoichiometric defect (d) F-centres On doping Ge metal with a little of In a one gets (a) p-type semi conductor () n-type semi conductor (c)_ insulator (d)_ rectifierClass-XII/Chapter-1/The Solid State 2 3 /@| 8 | @ | 13 | @) 4 [5 | @ | 10] &) [15 | @ Flints & Solutions 1. (b) Out of the given substances, only Li has 2178x103 -2.165x10 "0.013810? high electrical and thermal conductivity. = ; 7 . 2. (b) Liquid crystals on heating first become 2.17810 2.178x10" turbid and on further heating they become = 5.96 x 103 clear. £ Pyknometric density is the nearest to true 3. (@ Crystals show good cleavage because density calculated from the molecular mass their constituent particles are arranged in and crystalline lattice of the product. planes. 10. (b) Acp is a closed packed arrangement 4. (b) The phenomenon of occurrence of a in which the unit cell is hexagonal and substance in two or more crystalline structures coordination number is 12. is called polymorphism. 11. (a) Given: No. of A atoms at the corners of 5. (a) In 14 types of Bravais lattices, body jis eben” WE ae ceee te fe centred unit cell is present in cubic, tetragonal 8 and orthorhombic crystal systems. body centre = 1, Thus formula of the compound 6 (a) In CaF, the coordination numbers for is AB. Ca‘? =8 and F-=4 12, (a) Since MgO has a rock salt structure, each 7. (©) Givenr*= 100 pm cation is surrounded by six anions and vice Radius ratio of NaCl like crystal versa. 13. (b) For orthorhombic system a = B = y = 90° 14, (c) The total number of octahedral voids in FCC are four r= 100 =241.5pm Octahedral voids in FCC = Edge centres 0414 + Body centre 8. (a) For the given cubic structure, ‘The contribution of edge centre = *, Fraction of one edge centred*octahedral 1 No. of ¥atoms at the comers = 8x= void in one unit cell of FCC = i 15. (a) Let the number of atoms of element B= N No. of Yatoms at the face-centres = 6x y, (Formula of the compound = XY; So, the number of atoms of element A= Lx 2 ' (a) Fraction of unoccupied sites in NaCl 3 crystal -, The formula of the compound is Ay By ray density-pyknometric density = AB ri x-ray density So,x=2, y=3, xty=5 |lo. (a) Given: Edge Length (a) = 3.608 x 10-8 om Density of copper (d) = 8.92 In fcc crystal structure, the value of z is 4. zxM Naxa? 4xM =“ 6.022107? x(3.608%10°8)3 8.92 6.022%107 4 M M = 63.1 g/mol (Molar Atomic Mass) M= 63.1 u (Atomic Mass) 17. (a) Number of octahedral and tetrahedral voids formed by N closed packed atoms are N and 2N respectively, Hexagonal unit cell contains 6 atoms therefore, number of tetrahedral void= 2N =6 x 2=12 Number of octahedral void = N = 6 18. (d) Forbec, \3a=4r=> Ba 4 Given, a= 288 pm r Boss pm 19. (©) Oh void (C) - 15 No. ofions => 6™ 755: 6 2 1 4 30: 4 4r 20. (d) For bec lattice : Z=2,a= Be For fec lattice : Z= 4, a = 2V2r (ve © dooce (_ZM_ Nat feo , 2V2r) _ 3N3 21. (d) No.of A?*ions= x 46.96 x10-4 HCP (A) 22. 23. 24, 25. 26. 27, 28, Chemistry No. of BY ions =4 x 1=4 No. of atoms in cep, 1 1 2- 7 =f +6 oO xgr6xs Hence the formula of the oxide will be AB4O4 0t ABO. (a) Number of octahedral voids in cep is equal to effective number of atoms. In cep, effective number of atoms are 4 so, 4 octahedral voids. So, 1 octahedral voids per atom. (a) For fee structure, 2a = 4r 2408 2r (2r= Diameter) Diameter = 288.5 ~ 288 pm (a) For bec lattice, diagonal = aV3. The distance between the two oppositely charged ions = $j = 287.752 (a) Since Cu metal crystallises in a face centred cubic lattice a 36 = r=—==127.6=128pm wW2 22 ” (a) Since lithium metal crystallises in a body centred cubic crystal SS =151.98 pm 4 (b) Percentage of occupied space in a bec is given by 35pm PR, (Sc) = Vol occupied by unit cell 99 Total Vol. of unit cell 2x48 = 3x10 = 68% 4r (5 Percentage of free space in a bee is (100 ~ 68) = 32% (a) Following generalization can ® easily derived for various types of lattice arrangements in cubic cells between the edge length (a) of the cell and r the radius of the sphere, For simple cubic : aclass XI1/Chapter-I/The Solid State Forbody centred eubie: a =r oF . 1 For face centred cubic: a = 2V2r or r= a? Thus the ratio of radii of spheres will be simple : 29. (4) Number of atoms per unit cell = 1 ‘Atoms touch each other along edges. Hence a roe 2 (r= radius of atom and a = edge length) 43 Therefore % fraction = on Mh 0.5: ar 6 30. (©) _Inbody centred cubic lattice one molecule of CsBr is within one unit cell. Atomic mass of unit cell = 133 + 80=213 amu Volume of cell = a? = (436.6 x 10-}9)3 cm? Density = -2* N4xa? Density = 1x213, 6.021073 x (436.6)? x10 213x107 = = 4.25 g/cm? 6.02 (436.6) In the density formula, Z is number of particles Present ina unit cell and M is molar mass of that Particle, For any diatomic molecule like CsBr, Z=2 but for any mono atomic molecule like Li, Z= 1 for bcc lattice. An isolated fee cell is shown here, Each face 7 the cell is common to two adjacent cells. herefore, each face centre atom contributes 32. 33. 34, 35. 36. 37. only half of its volume and mass to one cell. ‘Arranging six cells each sharing the remaining half of the face centred atoms, constitutes foc cubic lattice. e.g., Cu and Al. (a) Given: Order of Bragg diffraction (n) = 2; Wavelength (A) =1 A and angle (6) = 60° Bragg’s equation: nA = 2d sin 8 2x 1=2d sin 60° => 2xl= 2a b> a=S arid 2 v3 (where d = difference between the scattering planes) (©) A body-centred cubic system consists of eight atoms at the corners plus one atom at the centre of cube. (©) For fec, the edge length of the unit cell, a=2r* +r) where, -- = Radius of anion & r* = radius of cation 508 = 2(r° + 100) => 7 = 154 pm (©) Fluorite has fec structure where metal ie. Ca?* occupies regular lattice point of fee structure and F~ occupies all tetrahedral voids. Hence each F~ is surrounded by 4 Ca** ion and each Ca?* ion surrounded by eight F- ion. (©) The no. of atoms is a unit cell may be calculated by the the formula Dg MONT oie. 8 124 where 7, = no. of atom at the comer m, = no. of atoms at body centre ny = no. of atoms at face centre, 1, = no. of atoms at edge centre. An fec crystal contains atoms at corer and at face =8 82 (a) Frenkel and Schottky defects are shown by ionic solids. Both are stoichiometric defects, Schottky defects -the density decreases Frenkel defects + density remains same. Vacancy and Interstitial defects are shown by non-ionic solids. Both are stoichiom . chi i 7 iometric = 4 atoms in a unit cell,38. -, 40. 41. 42. Vacancy defects —> the density decreases Interstitial defects > the density increases (A) - Gv), B) - Gi), (© - @, D)- Gd) All the above mentioned defects belong to point defects. (a) Assertion: For any kind of point defect, electrical neutrality is an essential condition, e.g., metal deficiency defect. Reason: This is correct but it does not explain the given assertion. () Nip.9g0 = (NP), (Nig 59x (0%), Net charge [x * 2] + [(0.98 —x) x 3] + 2 x 1]=0 x=0.94 Fraction of nickel existing as 0.94 Ni?* Ds = 0.959 = 0.96 (b) AgBr shows both, Frenkel as well as Schottky defects. (d) The semiconductors formed by the introduction of impurity atoms containing one elecron less than the parent atoms of insulators are termed as p-type semiconductors. Therefore, silicon containing 14 electrons has to be doped with boron containing 13 electrons to give a p-type semi-conductor. (b) For each Sr** ion added, one Na* ion is removed to maintain the electrical neutrality. Hence concentration of cation vacancies = mole % of SrCl, added = 10-4 mole % 44, 45. Chemistry = 623.10 6.023107 100” . Alkali metal halide may have excess metal ion if a negative ion is absent from its lattice site creating anion vacancy, which is occupied by electron to maintain electrical neutrality, The ‘vacancy’ occupied by electrons are called F-centres or colour centres. (@ ‘When the crystal is irradiated with white light, the trapped electrons in a hole absorbs photon for excitation from ground state to excited state, This gives colour to the compound. (a) If in an ionic crystal of the type 4°B, equal number of cations and anions are missing from their lattice sites so that the electrical neutrality is maintained. The defect is called Schottky defect. (a) When electrons are trapped in anion vacancies, these are called F-centres. e tve -ve a ion ion 6 F-eente in erystal (a) p-type of semiconductors are produced by adding impurity containing less electrons (ie. atoms of group 13). Ge belongs to Group 14 and In to Group 13. Hence, on doping, p-type semiconductor is obtained.Solutions ;{LOD|Qns.|LOD|Qns.|LOD) Topic Name Sub-Topic ____|Qns| ns |LOD| cer tion of solutic ir].# Solubiity and | C2R€eNtration of solution concentration of | effect of temperature on solutions molality/molarity/ mole fraction Raoult’s law 1/€ ‘Vapour pressure, law of solutions, ideal and non azeohrppes: al ideal solutions pdfrentre ata molality and ky Colligative properties : and abnormal Oapotic pressure ele molecular masses depression in alm freezing point i ane ey toda OE Bh and Concentration of Kj, value for some gases at the same temperature ‘T’ are given : NCERT| Page-41/ N-7 | RS 2022 Bas Kyj/k bar Ar 40.3 Co, 1.67 HCHO 1.83 x 10-5 CH, 0.413 Where Kj, is Henry’s Law constant in water. The order of their solubility in water is () HCHO separated solvent molecules, AH, (ii) Pure solute > separated solute molecules, AH, (ii) Separted solvent — Solution, AH, & solute molecules Solution so formed will be ideal if A solution containing components A and B follows Raoult’s law when (NCERM| Page-47//N-13 & 14) 2002 A~B attraction force is greater than A— A. and B-B A~B attraction force is less than A ~ A and B-B A~B attraction force remains same as A-Aand B-B Volume of solution is different from sum. of volume of solute and solvent ‘An ideal solution is formed when its ‘components NCERU| Page47/N-13 | jog (@) have no volume change on mixing (©) have no enthalpy change on mixing (c) have both the above characteristics (4) have high solubility, @ (b) © @)All form ideal solution except NCERT | Page N-14 & 15 1988 (a) CeH, and CgH, CH, (®) CyHg and C,H3I (© CHCl and C,H, Br @)_ CyHy land C,H, OH. | Topie-3: Colligative Properties and Abnormal Molecular Masses 30. 31. 32. 33, The following solutions were prepared by dissolving 10 g of glucose (CgH,,0,) in 250 mL of water (P,),10 g of urea (CH,N,O) in 250 mL. of water (P,) and10 g of sucrose (C)H,,0 ,,) in 250 mL of water (P3). The right option for the decreasing order of osmotic pressure of these solutions is : 2021 (@) Ps>Pi>Py —(b)- P,>P, > Py (c) P)>P)>P3 (d) Py>P3>P, The freezing point depression constant (K,) of benzene is 5.12 K kg mol. The freezing point depression for the solution of molality 0.078 m containing a non-electrolyte solute in benzene is (rounded off upto two decimal places) : (a) 0.80K (b) 040K (©) 0.60K (@ 020K 18 g ofa non-electrolyte solute is dissolved in 114 g of n-octane to reduce its vapour pressure of 80%, the molar mass (in g mol) of the solute is [Given that molar mass of n-octane is 114g mol") (NOER] Page-50 | 2020 (a) 20° (b) 40 ©) 60d) 80 If molality of the dilute solutions is doubled, the value of molal depression constant (Kj) will be:- 2017 (a) halved (b) tripled (c) unchanged (d) doubled At 100 °C the vapour pressure of a solution of 6.5 g of a solute in 100 g water is 732 mm. If K, = 0.52, the boiling point of this solution 2020 will be 2016 (a) 101°C (b) 100°C (c) 102°C (d) 103°C Which one of the following electrolytes has the same value of van’t Hoff’s fuetor (i) as that of the Al,(SO,), (if all are 100% ionised) ? 2015; Similar 1994 37. 38. 7m. 40, 41. Chemistry (@) Kj[Fe(CN),] —(b)_AI(NO,), © KylFe(CN)] @ K,SO, The boiling point of 0.2 mol kg~ solution of X in water is greater than equimolal solution of Y in water. Which one of the following statements is true in this case ? 2015 (@) Molecular mass of X is greater than the molecular mass of ¥. (&) Molecular mass of X is less than the molecular mass of ¥. (©) ¥ is undergoing dissociation in water while X undergoes no change. (@_Xis undergoing dissociation in water. Of the following 0.10m aqueous solutions, which one will exhibit the largest freezing Point depression? “2014 Similar 1991 (a) Kel ©) CoH, ,05 (© AL(SO,), (@) K,S0, ‘The freezing point depression constant for water is— 1.86 °C m™. IF 5.00 g Na,SO,j is dissolved in 45.0 g H,O, the freezing point is changed by = 3.82 °C. Calculate the van’t Hoff factor for Na,SO,. INCERT [Page-58 / N-24 [2011 (a) 2.05 (b) 2.63 © 3.11 @ 0381 The van’t Hoff factor i for a compound which undergoes dissociation in one solvent and association in other solvent is respectively : INCERT | Page-s8/N-24| 2011 (@) less than one and greater than one. (b)_less than one and less than one. (©) greater than one and less than one. (d) greater than one and greater than one. A0.1 molal aqueous solution of a weak acid is 30% ionized. If K, for water is 1.86 °C/m, thé freezing point of the solution will be : NCERP | Page-60 /1N-24 2011 (a) -0.18°C (b) —0.54°C (©) -036°C (@) 024°C 200 mL of an aqueous solution of a protei” contains its 1.26 g. The osmotic pressure ¢ this solution at 300 K is found to be 2.57 * 10 bar. The molar mass of protein will (R= 0.083 L bar mol! K-!) ao (a) 51022 ¢ mot! — (b)_ 122044.g mol! (©) 3101 gmot — (a) 61038 g mol! adClass-XII/Chapter-2/Solutions 4a 4B. i ‘An aqueous solution is 1.00 molal in KI Which change will cause the vapour pressure of the solution to increase? 2010M (@) Addition of NaCI (0) Addition of Na,SO, (©) Addition of 1.00 molal KI (@) Addition of water Assolution of sucrose (molar mass = 342 g mot-!) has been prepared by dissolving 68.5 g of sucrose in 1000 g of water. The freezing point of the solution obtained will be (K;for water = 1.86 K kg mol"), ‘NCERT | Page-58/N-24 [2010 M_ (b) - 0.520°C (d) - 0.570°C (@ - 0372°C @ + 0372°C . A-0.0020 m aqueous solution of an ionic compound Co(NH;)s(NO,)CI freezes at — 0.00732 °C. Number of moles of ions which 1 mol of ionic compound produces on being dissolved in water will be (K-= — 1.86 °C/m) 2009 (@ 3 @2 (b) 4 © 1 . 0.5 molal aqueous solution of a weak acid (HX) is 20% ionised. If Ky for water is 1.86 K kg mol ",the lowering in freezing point of the solution is 2007 (a) 056K (b) 112K ©) -056K @ -1.12K During osmosis, flow of water through a semipermeable membrane is |NCERT | Page'S/N-21 |2006 (2) from both sides of semipermeable membrane with equal flow rates (>) from both sides of semipermeable membrane with unequal flow rates from solution having lower concentration only from solution having higher concentration only () (d) * A solution containing 10 g dm? of urea (molecular mass = 60 g mol!) is isotonic with 45% solution of a non-volatile solute. The molecular mass of this non-volatile solute is NCERT | Page-56/ N-22 {2006 (4) 300 ¢ mor! (b) 350g mol! (9) 200 ¢ mol! (d) 250g mol! 1.00 g of a non-electrolyte solute (molar mass 2502 mol!) was dissolved in 51.2.g of benzene. 49. 50. 51. 2 54. If the freezing point depression constant, K; of benzene is 5.12 K kg mol", the freezing point ofbenzene will be lowered by 2006 (@) 03K (b) 05K () 04K (d) 02K Asolution of urea (mol. mass 56 g mol”) boils at 100.18 °C at the atmospheric pressure. If K and K, for water are 1.86 and 0.512 K kg mol! respectively, thie above solution will freeze at 2005 (@) 0.654°C (b) -0.654°C (©) 654°C (@ -654°C Camphor is often used in molecular mass determination because 2004 (@)_ itis readily available (b)_ ithas a very high cryoscopic constant (©) itis volatile (@) itis solvent for organic substances A solution contains non-volatile solute of molecular mass M,. Which of the following can be used to calculate the molecular mass of solute in terms of osmotic pressure ? 'NCERT | Page-S5 / N-27| 2002 RT @ a, -("\yer 0) i, -(™2 22 © M, -(2 er @ M (2) ‘The beans are cooked earlier in pressure cooker, because 2001 (a) Boiling point increases with increasing pressure (b) Boiling point decreases with increasing pressure (©). Internal energy is not lost while cooking in pressure cooker Extra pressure of pressure cooker, softens the beans Which of the following colligative property can provide molar mass of proteins (or polymers or colloids) with greatest precision ? 2000 (a) Osmotic pressure (b) Elevation of boiling point (c) Depression of freezing point (d)_ Relative lowering of vapour pressure A 5% solution of cane sugar (mol, wt, =342) is isotonic with 1% solution of a substance . ‘The molecular weight of X is 980 (a) 34.2 (b) 1712 © 684 @) 1368 @es 5 37. 6. 58. 59, The vapour pressure of a solvent decreased by 10 mm of mercury when a non-volatile solute was added to the solvent. The mole fraction of the solute in the solution is 0.2. What should be the mole fraction of the solvent if the decrease in the vapour pressure is to be 20 mm of mercury? NCERT | Page-49 | 1998 (@@) 08 (6) 06 (©) 04 (d) 0.2 The vapour pressure at a given temperature of an ideal solution containing 0.2 mol of a non- volatile solute and 0.8 mol of solvent is 60 mm of Hg. The vapour pressure of the pure solvent at the same temperature is 1996 (a) 150mmofHg (b) 60 mmofHg (©) 75mmofHg (4) 120mmofHg Vapour pressure of benzene at 30 °C is 121.8 mm. When 15 g of a non volatile solute is dissolved in 250 g of benzene, its vapour pressure decreased to 120.2 mm. The molecular weight of the solute (Mo. wt. of solvent = 78) 1995 (@) 356.2 (&) 456.8 (©) 530.1 @ 656.7 ‘According to Raoult’s law, relative lowering of ‘vapour pressure for a solution is equal to NCERT| PageN-15 & 16 1995 moles of solute moles of solvent (c) mole fraction of solute (d)_ mole fraction of solvent At 25°C, the highest osmotic pressure is exhibited by 0.1 M solution of 1994 (a) CaCl, (b) Kel (c) Glucose (a) Urea. @) (b) Chemistry 60. Which one is a colligative property ? NCERT | Page-49 / N-15 | 1992 (@) boiling point (6) _-vapour pressure (©) osmotic pressure (d) freezing point If 0.1 M solution of glucose and 0.1 M solution of urea are placed on two sides of the semi- permeable membrane to equal heights, then it will be correct to say that 9 ()_ There will be no net movement across the membrane (b) Glucose will flow towards urea solution (©). urea will flow towards glucose solution (@) water will flow from urea solution to glucose The relative lowering of the vapour pressure s equal to the ratio between the number of NCERT | Page-SO/N-15 & 16] 199! solute molecules to the solvent molecules solute molecules to the total molecules in the solution (c)_ solvent molecules to the total molecules in the solution (@)_ solvent molecules to the total number of ions of the solute. Which of the following aqueous solution hs ws minimum freezing point ? (@ 0.01 m NaCl () omsac ite (©) 0.005 m Mgl,, (d) 0.005 m MgSO; Blood cells retain their normal shape in seu which are (a) hypotonic to blood (b) isotonic to blood (©) hypertonic to blood (@)_equinormal to blood. 61. 62. @ () 63. 64, PEM onClass-XII/Chapter-2/Solutions Flints & Solutions 1. (0) Higher the value of Ky, lower is the 7. solubility of gas, correct order : HCHO > CH,> CO, > Ar Goo pressure over a solution indicates the less solubility or not favourable interaction of gas molecules with solvent molecules. = Ky ; large value of partial 2. (a) For one molal solution, 1 mol of solute should be present in 1000 g of solvent. Or we can say that 0.5 mol of solute should be present in 500g of solvent. 3. @ Let, volume of solution = 1 L Mole of NaOH = 2 Mass of NaOH solution = volume x density = 1000 x 1.28 = 1280 g % Mass of H,O = (1280-2 x 40) = 1200 g= 1.2kg Mole ofNaOH _ 2 Molality (mn) = =o olality (mm) = fags of solvent (kg) 1.2 =1.67m 4. (@) Molarity depends on the volume of a 1 solution which can be changed with change in temperature. 5 (d) 1.00 mie., 1 mole of solute present in 1 kg of water 1000 Moles of 1 = 10008 55.55 mole of kg H20 = 73 7 /mol Mole fraction =—Tolute 1 i. Meolute + Myater (1+55.55) = 0.01768 = 0.0177 6 wtx1000 12, (4) Molarity (M) = 2 Mt 1000 63” 250 & 7 8 ‘ol wt. x vol (mL) WL of 70% acid = ead 5 45 g (b) Concentration of 25.3 1000 106 350 = 0,955 M | [Na*]=2« 0.955=1.91M | [co¥ ] =0955M (©) Molarity of H,SO, solution __ 98% 1000 98x 100 Suppose V mL of this H,SO, is used to prepare 1 Lof0.1M H,SO, ©. ¥*180 = 1000 0.1 _ 1000%0.1 180 NayCO3, ~180-180 ay =5.55maL (©) From molarity equation M,V, + M,V,= MV 1*2.5+0.5*3=Mx55 M= 7 0.727 = 0.73M. 55 (b) Density = 1.17 g/ee __Mass ~ Volume volume = lec mass = 1.17g No. of moles of solute Volume of solution in litre 2117x1000 _ 1170 _ 30.05M 365x136. (a) The mole fraction can never be equal to -2 or 2. It is always between 0 and 1 ie, O Xan 5 andy Total pressure of solution (P)= Pox, + Ary 1 1 P= 128% > +3.85% > = 8.325 kPa 128x1 8.325 Yg=1-yq=1-0.768=0.232 so, the vapour will contain higher percentage of benzene. As the molar composition is same and benzene has higher vapour pressure, the vapour will contain higher percentage of benzene. = 0.768 () For an ideal solution AS,,;, > 0 Entropy will always increase upon mixing two compounds as disorder increases. () P=PAX,+PpXg= PiX4+Pp(1-X)) (for binary sol. X4+ X= 1) 3 Pt Py sat = Pat Xy(Ex-Pa) 255 _o213 (© Pettey = al 3 MCHC, = 2 = 0.47 Pr =P,X4+PpXq 9.213 | gig, 0.47, 0.683 0.683 = 62.37 + 285.5 = 347.9 mm Hg (a) A solution of acetone in ethanol shows positive deviation from Raoult’s law. It § because ethanol molecules has strong hydroge” bond, When acetone is added, the hydroge” bonds of ethanol becomes weaker. Therefor its volatility and vapour pressure increases. (8) Given P3= 80 torr Fon = 60 torr = Phx Xp+ P5XXo = 200x —— Protat = = fee = 1634122 55 Protat = 48 + 24 = 72 torr totalee Class-XII/Chapter-2/Solutions (0) Foran ideal solution, AFfyixing = 0 It means that no heat is evolved or absorbed when the components are mixed. 26. Hence, Aggy = AH, + AH, + AH. For ideal solutions there is no change in magnitude of the attractive forces in the two ‘components present. 77. (@) The two components A and B follows the condition of Raoult’s law if the force of attraction between 4 and B is equal to the force of attraction between A and A or B and B. 28. (©) For ideal solution, AV icing = 0 and AH rixing = 0. 28. (a) Ethyl alcohol forms hydrogen bonding with itself, hence it will not form ideal solution with CHI. 30. (b) Osmotic pressure (m) = iCRT where C is molar concentration of the solution. = ixmx1000%RT MxV Order of molar mass of solute decreases as Sucrose (342) > Glucose (180) > Urea (60) So, correct order of osmotic pressure of solution is P; >> moles of solute). 0 PI~P, _ Moles of solute Py Moles of solvent 31 22, = Bam _Waxmy PD Max, = SP _WaxM, Pp) M2 xm, ( Ap=pP-pil Here W, and W, are the masses and My and 2 are the molar masses of the solvent and ‘olute respectively. 33. 34, 38. 36.° 37. => M)= =40g mol! 8x100 2 (©) Ky (molal depression constant) only depends on the nature of the solvent and is independent of the concentration of the solution. (a (Poh) 2 KM ~ N M W Where, 7, = wt of solute W, = wtof solvent M, M, = Mass of solvent at 100 °C, P° = 760 mm Mass of solute 760-732 __6.5x18 760 M,x100 M, =31.75 g mol _ WH x1000 ATy=m*Ky= Te, “Ko any = 252%65%1000 1 9506 31.75%100 boiling point of solution = 100°C + 1.06 °C = 101 °C (©) K,[Fe(CN),] <2 4K* + [Fe(CN),]- and Al,(SO,); > 2AI5* + 380?- “+ van't Hoff factor is 5 for both Al, (SO,) and K,[Fe(CN),] (d) AT, =iK,m Given, (A7,)y>(AT))y . iyK,m>iyK,m (K, is same for same solvent) iy>iy So, X is undergoing dissociation in water. (©) Colligative properties & no. of particles, Since Al,(SO,); contains maximum number of particles, hence will have the largest value of freezing point depression,39, 40. 41. 42. 43. 44, (b)_ Given K-=- 1.86° cm, mass of solute = 5.00 g, mass of solvent = 45.0 g AT;=i* Kem saital x 82 =i x 1.86 BBD= E186 x Ts (Molecular mass of Na,SO, = 142) 1=2.63 (©) Tfcompound dissociates in solvent #> 1 and on association /< 1. (@) Given o=30% ie.,0.3 HA —> H*+A~ laa a 1-03 03 03 i= 1-03+03+03 i=13 AT, = iKym 1.3 x 1.86% 0.1=0.2418 T, = 0-0.2418 =— 0.2418 °C (@_7=CRT Osmotic pressure) tO ar =2.57% 103 Molecular mass 1.26%1000 ——— ie 00 Mol.mass x 200 pOneaxs 1.26x0.083%300x1000 200x2.57x10> = 61038 g mol! (d) When the aqueous solution of one molal KI is diluted with water, concentration decreases, therefore the vapour pressure of the resulting solution increases. 100077, Mm, _ 186*1000%68,5 ““3aax1000 = 372°C T= 0- AT) =-0.372°C (d) AT; =0-(-0.00732°) = 0,00732 AT, =1*K, Xm n= Molecular mass = (a) AT =K, 45. 46. 47. 48. 49, Chemistry (b) ASAT, =iKym For . HX == Ht + x oo4 0 ° eq (10.20) 0.20 i; 020 Total no. of moles = 1 — 0.20 + 0.20 +0.20 AT, =1.2* 1.86 x 0.5= (b) During osmosis, water flows through semipermeable membrane from both. sides but the net flow is from solution having lower concentration to higher concentration. . RT (a) _Osmotie pressure = x= cRT => x=" 5% solution means 100 mi 1000 ml For isotonic solution, x=, 50 ox 0821xT =—x.0821xT (V=1 dm? = 1 litre) M=300 gmot! © AT = Kym =5.12% 1.100 oak 250 512 (0) ASAT,=K;.m AT, =K,.m Hence, we have m=. Se Ky Ky K, or AT, an K, => [AT,= 100.18 - 100 = 0.18°C] 1.86 = 0.18x >. = 0.654% 0512 0.654°C As the Freezing Point of pure water is 0°C, AT; = 0-7, 0.654=0- 7, T, =- 0.654 Thus the freezing point ‘of solution will be -0.654°C,Class-XII/Chapter-2/Solutions 50, (b) Solvent having high cryoscopic constant ; én can be used in determination of molecular > mole fraction of solute = — scopic method. mui ee => Mole fraction of solute = 0.4 si. (0) kV =nRT=2RT or My = (@} Hence, mole fraction of solvent = 1 - 0.4 = 0.6 sl M Vv 7 Decrease in vapour pressure oc Where M, = molecular mass of solute Mole fraction of solute. and m, = mass of solute 51. (a) The beans are cooked earlier in pressure 56. (c) Given: boiling point increases with ; zo facrtg preenre: — Xp =Mole fraction of solute = 2-2 — 0.2+08 5 53. (a) Molecular masses of polymers are best determined by osmotic pressure method . Because other colligative properties give so low values that they cannot be measured accurately. fi Osmotic pressure measurements can be made RT P=60 mm of He Relative lowering vapour pressure atroom temperature and do not require heating which may change the nature of the polymer. 54 (©) 5% cane sugar solution means 100ml of solution contain cane sugar = Sg . 1000 mL. of solution contain cane sugar 57+ (@)_ Given vapour pressure (p?) = 121.8 mm; Weight of solute (w) = 15 g Weight of solvent (7) = 250 g From Raoult’s law, 3 = 7991000 = Sog/L Similarily 1% solution contains P°-P_w M_1218-1202 15. 78 _ 1000 _ a a BM 1218-1202 15 78 =O 10 pot x Pom W128 ~ m* 259 As both are isotonic, or m= 15X78 121.8 _ 3565 So M=M 250 1.6 “ orC,RT=CRT 58. (©) Relative lowering of vapour pressure st depends upon the mole fracti on Bs 10, eer ends yon the mole action of sole, M wa ie, mole fraction of solute M (mol. wt. of X) = = = 68.4 7 s 59. (a) Cone. of particles in CaCl, sol. will be 55, Zn?*(aq) + Cu(s) is 1.1 V. Calculate the standard Gibbs energy change for the cell reaction. (Given F = 96487 C mol"! (a) -200.27J mot (2) -200.27 kJ mot! (c) -212.27kJ mol! (d) -212.273 mol"! Given below are half cell reactions: MnO +8H* +5e” > Mn* +4H,0, $2 +2H* +2e” +H,0 EB =+1,223V (0/0 Will the permanganate ion, Mn Qj liberate O, from water in the presence of an acid? INGER |Pages69 /1N-34 (2022 (a) No, because E,.y, =~ 0.287 V ° 37, (b) Yes, because E,.y =+ 2.733 V (©) No, because B,<1 = 2.733 V (d)_ Yes, because Ey = + 0.287 V 32. 35. 36. Chemistry Find the emf of the cell in which the following reaction takes place at 298 K_ (NCERT | Page-70/N-38)2H03 Ni(s) + 2Ag* (0.001 M) > Ni?* (0.001 M) + 2Ag() (Given that Ej, = 1osy,2208E = 0.059 at 298K) (@ 1385Vv (b) 0.9615 V © 1.05V @ 1.0385 v For a cell involving one electron Ey, = 0.59 V at 298 K, the equilibrium constant for the cell reaction is : a [ 2Fe?* (aq) + L(aa) 0.24 V at 298 K. The standard Gibbs energy (A, G®) of the cell reaction is: i [GiventhatFaraday constant F=96500C mol | (@) ~46.32kJ mol"! (6) -23.16 kJ mol" (©) 46.32kI mot! —(d)_ 23.16 kJ mol In the electrochemical cell :~ 20K siiiia00 Zn | ZnSO, (0.01M) | | CuSO, (1.0 M) | Ch the emf of this Daniel cell is E,. When the concentration of ZnSO, is changed to 1.0M and that of CuSO, changed to 0.01M, the emf changes to E,. From the followings, which one is the relationship between £, and £, Given, 87 = 9,059) @ 2 <2, (b) £,>E; © £,=048, @) £,=E The pressure of H, required to make the potential of H,-electrode zero in pure water # 298 K is : oa (a) 10-4 atm (b) 10" atm (c) 10°! atm (d) 04am A hydrogen gas electrode is made by dippit8 platinum wire in a solution of HCI of pH = 10 by passing hydrogen gas around the platinu® wire at one atm pressure, The oxidation potent of electrode would be ? = (@) 059V (©) Li8v (b) O.118V (d) 0.059.Vclass-XI1/Chapter-3/Electrochemistry 38, Consider the half-cell reduction reaction : 40. al, a. Mn2* + 2e" > Mn, E°=-1.18 V Mat -» Mn?* +e, E?=-1.51V The E° for the reaction 3Mn?* > Mn? + 2M", and possibility of the forward reaction are, respectively * (Kak 2013 () -2.69Vandno (b) ~4.18 Vand yes (:) +033 Vandyes (d) +2.69Vandno 39, Standard electrode potential of three metals X, Vand Z are ~ 1.2 V, + 0.5 V and ~ 3.0 V, respectively. The reducing power of these metals will be : oni (a) Y>Z>X (b) X>¥>Z (@ Z>x>¥ (d) X>Y>Z The electrode potentials for ao Cu?*aq) + 7 —> Cu"(aq) and Cu*(aq) +e” —> Cu(s) are + 0.15 V and + 0.50V, respectively. The value of E°Q.2 jo, Will be @) 0.s00V (b) 0325V (©) 0.650V (@ 0.150V Standard electrode potential for Sn‘* / Sn?* couple is + 0.15 V and that for the Cr3* / Cr couple is - 0.74 V. These two couples in their standard state are connected to make a cell. The cell potential will be : (ont @ +1I9V (b) +0.89V ©) +018V @ +183V Ifthe E°..y for a given reaction has a negative value, then which of the following gives the comet eationships forthe values of AG* and 2 (@) AG?>0;K,>1 ) aGr<0;Ke>1 © a@0; ik. <1 * A solution contains Fe?', Fe>* and I” ions. This solution was treated with iodine at 35°C. 2 for Fe3* / Fe2* is + 0.77 V and E° for 1,21 =0.536 V. The favourable redox reaction is: |NCERT [Page-78/)N-34 [2011 M (2) 1, will be reduced to I~ () ‘There will be no redox reaction (©) F will be oxidised to 1, (4) Fe will be oxidised to Fe™* 44, 45. 46. 47. 48. 49. For the reduction of silver ions with copper metal, the standard cell potential was found tobe + 0.46 V at 25°C. The value of standard Gibbs energy, AG° will be (F = 96500 C mot!) 2010 (@) - 99.0%) (b) - 89.0) () - 4450 (@ - 980k) Consider the following relations for emf of a electrochemical cell: 2010 (emf of cell = (Oxidation potential of anode) — (Reduction potential of cathode) (i) emf of cell = (Oxidation potential of anode) + (Reduction potential of cathode) (éi) emf of cell = (Reduction potential of anode) + (Reduction potential of cathode) (iv) emf of cell = (Oxidation potential of anode) - (Oxidation potential of cathode) Which of the above relations are correct? (@) (i) and (iv) (b) Gi) and (i) (© @ and Gi) @ ii) and Gv) Given: 2009 () Cut +26" Cu, B= 0.337V (i) Cu +e° > Cu’, B= 0.153V Electrode potential, F° for the reaction, Cu* +e" Cu, will be : (@) 0.90V () 030V (© 038V @ 0.2V On the basis of the following E° values, the strongest oxidizing agent is 2008 [Fe(CN),]** > [Fe(CN) > +e"; E°=-0.35V Felt Fed +e E°=-0.77V (@) [Fe(CN)J+ (bo) Fee (c) Fe* (@)_[Fe(CN),)>- The equilibrium constant of the reaction: Cu(s) + 2Ag*(aq) —> Cu?*(aq) + 2Ag(s); E° = 0.46 V at 298 K is ia007 (a) 2.0 10!0 (b) 4.0 x 1910 () 4.0.x 10! (d) 24x 1010 If Bip = OAM and Bay ae = +0.771Y, the standard EME of the reaction Fe +2Fe3* > 3Fe? willbe N34] 2006 (a) 1653 ) 1212 (©) O.1NV @) 0330V ee”50. 52. 54. 55. A hypothetical electrochemical cell is shown below A| At (XM) || B* (yM) |B The emf measured is +0.20 V. The cell reaction is 2006 @ Atte A Bt oB (6) The cell reaction cannot be predicted (©) A+BY>A*+B () AY+B>A+Bt The standard e.m.f. of a galvanic cell involving cell reaction with n = 2 is found to be 0.295 V at 25°C. The equilibrium constant of the reaction would be (NCERT | Page"73//N39 (2004 (Given F=96500C mot"! 314JK" mol!) (@) 20x10" (b) 4.0 10! (©) 1.0 102 @ = 1.0x 1019 On the basis of the information available from the reaction 4 2 zAl+02 > ZAl203, AG = ~ 827 KJ mot! of O,. The minimum e.m-f required to carry out an electrolysis of ALO, is (F = 96500 C mol!) 2003 (@) 856V (b) 2.14V (©) 428V @ 642Vv Which reaction is not feasible? 2002 (a) 2KI+Br, > 2KBr +1, () 2KBr+ 1, > 2KI+ Br, (©) 2KBr+l, > 2KCI+ Br (@ 2H,0 + 2F, > 4HF +0, Standard electrode potentials are ; Fe2+/Fe [E°=~ 0.44); Fe**/Fe®* [£°=+ 0,77] ; If Fe2*, Fe** and Fe blocks are kept together, then 2001 (a) Fe?* increases (b) Fe decreases 2+ Fe (©) 7 remains unchanged re (d) Fe?* decreases Cu(aq) is unstable in solution and undergoes simultaneous oxidation and reduction according to the reaction ; 2000 2Cu* (aq) = Cu" (aq) + Cus) choose correct £” for above reaction if E° (Cu?*/Cu) = 0.34 V and E° Cu2*/Cut = 0.15 V 56. 58. 59, 60. Chemistry (@) -038V () +049V (© +038V @ 0.19 What is the £°, ,, for the reaction Cu?* (aq) + Sn?* (aq) += Cu(s) + Sn fa) at 25°C iff the equilibrium constant for the reaction is 1 x 105?/NCERT |Page-73/N-39]19) (a) 0.5328 V (b) 0.3552V. (c) 0.1773 V @) 0.7104V For the cell reaction, 1998 Cu* (C,, aq) + Zn(s) = Zn?* (C,, aq) + Culs) of an electrochemical cell, the change in fiee energy, AG, at a given temperature is a function of @ mC) (b) In(CyC,) (© nC) (@) In(C,+C,) Without losing its concentration ZnCl, solution cannot be kept in contact with 198 (a) Au (b) Al) Pb (d) Ag E for the cell, Zn | Zn?* (aq) || Cu* (aq)|Cuis 1.10 V at 25°C. The equilibrium constant for the cell reaction: Zn + Cu (aq) ——Cu + Zn** (aq), is ofthe order of — (NCERT/Page-73/N39|1"” (@) 10-8 (&) 10°57 (1018 (@) 107 Standard potentials (£°) for some half-reactions are given below : it (1) Sn#*+2e-~ Sn2*; Fe=+ 0.15 V (2) 2Hg?* + 2e- > Hg?*; B= +0.92V (3) PbO, + 4H* + 2c 2P2* + 2H,0; P+l: Based on the above, which one of the followin statements is correct ? (a) Sn Pott is a stronger oxidising agent tha (b) Sn?* is a stronger reducing agent the” He2 (c) Hg? is a stronger oxidising agent th" Pot (@) Pb is a stronger reducing agent th" sn2*class-XIl/Chapter-3/Electrochemistry «i, The comect relationship between free energy and equilibrium constant K of a reaction is NCERT | Page-74/N-40 | 1996 (a) AG?=-RTInK (b) AG=RTInK () AG=RTInK = (4) AG=-RTInK 62, An electrochemical cell is set up as: Pt; H, (latm) | HCI@.1 M) || CH,COOH (0.1 M)| H, (latm); Pt, The e.m.f of this cell will not be zero, because 1998 (a) the temperature is constant (b) em.fdepends on molarities of acids used (©) acids used in two compartments are different (@ pHof0.1 MHCland 0.1 M CH,COOH is not same . When CuSO, is electrolysed using platinum electrodes, 1993 (a) Copper is liberated at cathode, sulphur at anode Copper is liberated at cathode, oxygen at anode ‘Sulphur is liberated at cathode, oxygen at anode (@) Oxygen is liberated at cathode, copper at anode | The standard reduction potentials at 25°C of Li*/ Li, Ba?* / Ba, Na* Na and Mg?* /Mg are ~ 3.03, ~ 2.73, — 2.71 and — 2.37 respectively. Which one of the following is the strongest oxidising agent? |NCERT|Page-71//N-341|1994 (@) Nat (6) Lit (¢)_Bat* (@) Mg* 0) € Topic-4: Commercial Cells and Corrosion ‘S. Adevice that converts energy of combustion of fuels like hydrogen and methane, directly into lectrical energy is known as : oma () Electrolytic cell (b) Dynamo © Ni-Cd cell (@) Fuel Cell 66. 67. 68. 69. 70. m1. A button cell used in watches functions as following : Zn(s) + Ag,0(s) + H,0() —= 2Ag(s) + Zn?*(aq) + 20H-(aq). If half cell potentials are : Zn?*(aq) + 2e- -> Zn(s); E°=- 0.76 V Ag,0(s)+H,0 (I) + 2e"—> 2Ag(s) +20H (aq); E=034V The cell potential will be : 2013 (a) 042V (b) 0.84V (©) 134V @ 110Vv Standard free energies of formation (in kJ/mol) at 298 K are ~ 237.2, — 394.4 and — 8.2 for H,O(1), CO,(g) and pentane (g), respectively. The value of E°,,. for the pentane-oxygen fuel cell is: 2008 (a) 1.968V (b) 2.0968 V (©) 1.0968 V (a) 0.0968 V The efficiency of a fuel cell is given by 2007 AG AG AS AH @ e (b) rT; (©) AG @ AG In the silver plating of copper, K[Ag(CN),] is used instead of AgNO. The reason is 2002 (@) A thin layer of Ag is formed on Cu (0) More voltage is required (©) Ag* ions are completely removed from solution (@) Less availability of Ag* ions, as Cu cannot displace Ag from [Ag(CN),}- ion The most convenient method to protect the bottom of ship made of iron is 2001 (a) Coating it with red lead oxide (b) White tin plating (©) Connecting it with Mg block (@ Connecting it with Pb block The most durable metal plating on iron to protect against corrosion is 1994 (a) nickel plating —(b) copper plating (0) tinplating (@)_ zine plating.© |-9 | @ | 17| © | 25] @ | 33 | © Chemistry () () () @ @ © (o) @ © | 10] © | 48 | © ©) | 34] @ t | (@) | 19 | @ | 27 | @ | 35] ©) 12 | (@) | 20 | (a) | 28 | (b) | 36| (a) ) | 21 | ©) | 29] & | 37] @ ) | 14] @) | 22] @ [30] © [38] @ &) | 15 © [23] © | 31] @ [39] © @ | 16] @ [247 @ | 32] &) [40] ©) (o) @ @ © @) (b) (b) () @ (o) @ @ | @ (a,b) @) © © (o) () @ © (©) @ Fiints & Solutions 1. (©) Conductivity = conductance * cell constant cet R £ =k R=0.0210 x 60 = 1.26 cm 2. (©) According to Koblrausch law of independent migration of ions. Am (CH3COOH) = Af, (CH3COONa)+ A, (HCI)—A, (Nacl) =91.0 S cm? mol + 426,16 S em? mol! — 126.45 S cm? mot! = 390.71 S cm? mot! 3 @ AScu,coon *Scx,coo- + Abu = 50 +350 = 400 S em? mol! 2 2 SS 0, (g) + 4H” (aq) +4e (@)_Lequivalent of any substance is deposited by 1 F of charge. 20 g calcium contains, . Given mass ‘Number of equivalents = ———— Equivalent mass Equivalent mass of Ca = Mom mS = — = 20 Valency 2 Number of equivalents 3 1 So, | Faraday of charge is requited to deposit | equivalent of Ca. 6) G7) (©) Mn037 —>Mn0j +e7 0.1 mole Quantity of electricity required = 0.1F = 0.1 x 96500 = 9650 C (@) Wo, = "0, *Mo, 5600 2 “22400 = 1 equivalent of Ag = 108 (c) Applying, x32=8g=1 equivalent of O, Elt 96500 9 Equivalent weight of cobalt (Il) = = I=10A Time (1) = 109 min = 109 * 60 sec Substituting these values we get, | 591010960 _ 49 9 2x96500 a) AsQ=Ixt 2 = 4.0 x 104 x 6 x 60 x 60C = 8.64 x 108C 25. 26. 27. Chemistry Now since 96500 C liberates 9 g of Al 9 96500 =8.1 104g of Al (@ No. of g. eq. of H*=No. of eq. of mass _4.5_ Eqw 9 8.64 x 108 C liberates= 8.64%108 gal 3+ = 0.5 (Eq, wt of AP* -2=9 No. of g eq. of H* =no. of mole of H* Hence, Mass of H* = 0.5 x 1g =0.5g We know that, 2g H, at STP = 22.4L 0.5 gH, at STP = 24.05 =56L (b) If mercury is used as cathode, H* ions are not discharged at mercury cathode becaus? mercury has a high over voltage for hydroge?- In electrolysis of NaCl, following ionisations take place: NaCl—> Nat +r 1,0 211+ on Nat and Ht ions move towards cathode. However, only H* ions are discharged more readily than Na* ions because in electroche series, hydrogen is lower than sodium. At cathode : 2H* + 2e°-—> H,(g) If mercury is used as cathode, then Na’ ions a discharged at cathode in preference to H" ions yielding sodium, which dissolves in mercuy to form sodium amalgam. At cathode : Na* + > —> Na(s) ‘Na(s) + Hg(s) —> Na - Hg(s) W__4 a) By Faraday's 1S Law, —=—7— a E 96500 (where Q = /t= total electric charge) We know that no of equivalent Witt _1x965_ E 96500 96500 100 (where i= 1 A, 1= (16 x 60) + 5=965 86°) Since, we know that =0.01 no. of equivalent _ 0.01 9,91 Normality = 7 Volume (in litre) | aclass-XII/Chapter-3/Electrochemistry aL. (b) Given current (i) = 0.5 A; Time (f) = 100 minutes 6000 sec Equivalent weight of silver nitrate (E) = 108, ‘According to Faraday's first law of electrolysis Elt__108x0.5x6000 “96500-96500 (b) The value of A,G depends on n value as per the equation A,G =—nFE,.y So, assertion statement is correct Ey is an intensive property while A,G is an extensive thermodynamic property So, reason is correct but not explaining the assertion. = 3.3575 g. | (©) AG°=-nFE®,,, ==2 x 96500 x 1.19 mor? =~212.300 kJ mol! @ [MnO +8H* +5e" > Mn?* + 41,0 }x2 = v4n05/Mn2* =+1.510V [#0 > $02 +2H* + ae" xs E'y,0/0) =~1.223V 2Mn0j +6H* -> 2Mn?+ +50, +3H,0 1.510V—1.223V = 0.287 V * (b) Nis) + 2Ag* (0.001 M) > Ni*? (0.001 M) + 2Ag(s) Fag ™ Egy 292 jog NEAT Age Eay= 9, 109 eel = 1.05-—— 2 eBoy ~ 15205 9 opio* = 1.05- a ‘3 “0s6isy Me) ge. _ 2.303 ) Ejgy = 23OBRT oy x nF G ° ven: Be =0.59V n= 1 0590089 bee k 34, 35. 36. 37. 0.59 ose 718K =logk = 10910 (a) AG =-nFE° =-2 x 96500 x 0.24 =— 46320 J/mol =~ 46.32 kI/mol (b) For cell, ZnlZnSO,(0.01 M) || CuSO,(1.0 M)|Cu = Bey —230BRE loglZn?*] fen nF [cu] 3 2.303RT. (0.01) = Beg log When concentrations are changed for ZnSO, and CuSO,, we can write 2.303RT 1 x los Spe, Soe log —— E2 =E° cet oF 8 O01 E,>E, (a) 2H"(aq) + 2e° > H,(g) P; pape — 20591 jog Pie 2 (ate Pa, 0 = 00.0295 log —“2 5 ao'y Fy eo = 10-4 atm Bs H, —> 2H* + 20> Jat 19-10 1052 RE. 20-2952 og ao7!?y Ha/H ) Eat =+ osov (a) AB? = Btgg + Eogig =~ E81 - 1.51 =-2,69 Since AE? is negative v. AG? = -nFE®, AG? will have positive value so, forward reaction is not possible. The value of electrode potential of a half-cell reaction does not depend on stoichiometric co-efficient. e.g. Mn2*—> Mn** +; E°=-151V 2Mn?* —> 2Mn3* + 2e"; E° =— Ls39, 40. 41. 42. 43. 44. (©) Asthe value of standard reduction potential decreases the reducing power increases i.e., Z> xX >y¥Y 3012) G05) (b) Cu2* + le“ Cut; Ef =0.1SV;AGP =-mEPF Cut + le“ Cu; EQ =0.50V;AG3 =-n ESF Cu + 20° > Cu AG? = AG? +AG°, = nF? F=-1n, E,9 F+(-1)n, Eo F po MEL MEF _ 0.15x1+0.50%1 n 2 => 0325V ‘When exchange of electrons (n) is different for all three reactions, we can not use the formula for standard electrode potential (E,..). e.8., Cutt +e —> Cut (n= 1) Cutter" Gu (n=) Cut +20" —> Cu_(n=2) Ettice (b) The couple for which SRP value is high, will actas cathode and the other couple will act as an anode. # Ba ticut + Eextcy Eeett = Ecathode ~ Eanode = 0.15 V (0.74 V) = 40.89 V (d) Standard Gibbs free energy is given as AG? =~ nEF If By 0 Further AG? =—RT'In K,, AG? > O when K,, <1 (©) Given Fe*3/Fe?* = + 0.77 V and 1,/ 21° = 0,536V Reduction potential of Fe** / Fe?* > 1, / 1°, so Fe3* will be reduced and I- will be oxidised, (a) Cu+2Ag" (aq) —> Cu?* (aq) + 2Ag(s) Foy =+0.46V -2x0.46«96500 1000 Here,n=2, AG? =-nE°F. kJ=-89 kJ 45, 4. 48. 49, 50, Chemistry (2) Eis Ecatade ~ Panode > Fea = Fretteatrode ~ Freenode e aie ~ Bont Eng Hence, option (a) is correct. (d) Cu + 2e> > Cu; AG? =-nE°F =-2 Fx 0.337=-0.674F ll) Cul > Cu? +>; AG? =—nE? F =-1*Fx-0.153= 0.153F (i) On adding eqn (i) & (ii) Cut +e" > Cu; AG? =— 0.521 F=—nk'F, Here n= 1 E'=+052V (©) From the given data we find Fe* = +077) is strongest oxidizing (Ee (Fe**) agent. More the positive value of reduction potential, more is the tendency to get reduced (betet oxidising agent). (© As Beg =o PM iog x, : 0. oe » 0.46 = tog K, “Ol 0591 or K,=Antilog 15.57=3.7 x 1015 24 * 10" 6) Fe —+ Fe2* + 2e [Anode], E=-0.441V (Fe++¢-— > Fe] x2 [Cathode]: E=+0.771N Fe + 2Fe?* —> 3Fe2+ (overall) Foon = Eeathode ~ EXnode = 0.771 = (-0.441) = 0.771 + 0.441 = (c)_ The cell reaction is as follows : AvAtte Br+e>B Adding A+B" A*B 0.0591 (d) —logig K Here, n = 2, E° = 0,295 2x 0,295 logig K = 2025 eo 0.0591