New TUTORIAL SHEETS

CHEM 103

FUELS & THERMOCHEMISTRY

1. If 1g of fuel was heated at 1100C for 1hour in oven than 0.8g of fuel was left. The fuel was heated in muffle furnace for 7min at 9250C, with lid. The left over fuels weighs 0.65g. The fuel was strongly heated for more than 30min at 7350C in muffle furnace. The remaining residue weighs 0.35g. Proximately analyze the fuel and express the percentage of different components in it based on the data. \2. A sample of coal containing 89% C, 8% H and 3% ash was tested for its calorific value in bomb calorimeter. The following results were obtained:

Weight of coal burnt = 0.85 g Water equivalent of the calorimeter = 2500 g Water taken in the calorimeter = 650 g Observed rise in temperature = 2.5°C Cooling correction = 0.03°C Acids correction = 50 cal Fuse wire correction = 10 cal

3. Assuming the latent heat of condensation of steam as 580cal/g, calculate the gross calorific value and net calorific value of coal.

4. The composition by volume of a certain fuel sample is H2= 25%, CO = 6%, CO2 = 8%, CH4 = 15%, C2H6 = 11%, C2H4 = 20%, O2 = 2%, N2 = 2% and rest is ash. Calculate the amount of air required at room temperature and 750 mm pressure for complete combustion of 1m3 of the fuel.5. One gram of a coal sample was burnt in the current of oxygen in a combustion apparatus and further passed through two tubes containing known weight of KOH and CaCl2. The increase in weight of KOH and CaCl2 tube was 2.50 g and 0.55 g, respectively. Calculate the percentage of carbon and hydrogen present in the coal sample.

7. Explain why:A. An ideal fuel should have moderate ignition temperature.B. Gross calorific value is more than net calorific value.

8. Calculate the heat of formation of benzene at 270C, if the heat of combustion of benzene, carbon and hydrogen are -780.9, -94.05 and -67.23 Kcal/mole respectively.

9. In a moving boundary experiment 0.01 M solution of hydrochloric acid was treated with cadmium chloride solution. The nozzle used had a radius of 0.75 cm, when a current of 25

milliamperes for 30 minutes, the H+ ion – Cd+2 ion boundary moved through 23 cm. calculate the transport number of H+ and Cl- ions in hydrochloric acid solution used?

10. A sample of coal contain C = 90%, H = 8.9% and ash = 3%. The following data was obtained when the coal was tested for calorific value in bomb calorimeter: Weight of coal burnt = 1g, Weight of water taken = 2500g, Rise in temperature = 250C, Mean specific heat of apparatus = 0.098, acid correction = 50.0cal, Fuse wire correction = 10 cal. Calculate the gross and net calorific values of coal sample given that latent heat of condensation of steam is 587 cal/g

11. Explain in detail how you will do proximate analysis of given sample of coal.

12. Discuss the variation of molar conductancitivty with concentration for strong electrolyte and weak electrolyte.

13. Calculate the volume of air (volume % of oxygen in air = 21) required for the complete combustion of one liter of carbon monoxide.

14. When one mole of liquid benzene is completely burnt in O2 at constant pressure to form liquid water and CO2 gas, ∆H is -781 Kcal at 25oC. Calculate the heat of this reaction at constant volume at the same temperature. (R = 2 Cal/K/mol).15. The standard heat of formation of C2H5OH(l), CO2(g) and H2O(l) are -277, -393.5 and -285.5 Kj/mol respectively. Calculate the standard heat change for the reaction

C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)

16. Calculate ∆H for the reactionCH2=CH2(g) + 3O2(g) 2CO2(g) + 2H2O(l) at 25oC.Given the bond energies in KJ/molC-H 416.2 O-H 464.4O=O 493.7 C=C 615

C=O 711.3

17. 0.4 g of an organic compound was kjeldahlised and ammonia evolved was absorbed into 50 ml of seminormal solution of sulphuric acid. The residual acid solution was diluted with distilled water and the volume was made upto 150 ml. 20 ml of this diluted solution required 31 ml of N/20 NaOH solution for complete neutralization. Calculate the % of nitrogen in the compound.

18. Using the data ( all values are in kcal/mole at 25oC) given below, calculate the bond energy of C-C and C-H bonds

(i) ∆H combustion of ethane (C2H6) = -372(ii) ∆H combustion of propane (C3H8) = -530(iii) ∆H for C(graphite) C(g) = 172(iv) ∆Hf

o for H2O(l) = -68(v) ∆Hf

o for CO2(g) = -94(vi) Bond energy of H-H = 104

Ans - E C-H = 99 kcal/mole, E C-C = 82 kcal/mole (Arora-704)

19. Calculate the heat of formation of one mole of CH3CHO, using the data given below. Heat of vaporization of C(s), i.e. C(s) C(g) = 170 kcal. Bond energies are C-C = 80 kcal, C-H = 98 kcal, H-H = 103 kcal, O=O = 118 kcal, and C=O = 173 kcal

20. The heat liberated on complete combustion of 7.8 g benzene is 327 kj. This heat has been measured at constant volume and at 27oC. Calculate the heat of combustion of benzene at constant pressure. (R= 8.3 j/K/mole)

21. The molar heat of formation of NH4NO3(s) is -367.54 kj and those of N2O(g) and H2O(l) are +81.46 kj and -285.78 kj respectively at 25oC and at 1atm pressure. Calculate ∆H and ∆E for the reaction NH4NO3(s) N2O(g) + 2H2O(l)

22. An athlete is given 100 g glucose of energy equivalent to 1560 KJ. He utilizes 50% of this gained energy in an event. In order to avoid storage of energy in body, calculate the weight of water he would to perspire. Enthalpy of water for evaporation is 44 KJ/mole.

23. An athlete takes 20 breaths per minute at room temperature. The air inhaled in each breathing is 200 ml, which contains 20% O2 by volume, while exhaled air contains 10% O2 by volume. Assuming that all the O2 consumed is used for converting glucose into CO2 and H2O(l). How much glucose will be burnt in the body in one hour and what is the heat produced? (Room temperature is 27oC and enthalpy of combustion is -2822.5 KJ/mole at 0oC).

24. Assume that for a domestic hot water supply 150 Kg of water per day must be heated from 10oC to 65oC and gaseous fuel propane C3H8 is used for this purpose. What moles and volume of propane in litres at STP would have to be used for heating domestic water. Enthalpy of combustion of propane is -2050 KJ and specific heat of water is 4.184 x 10-3 KJ/g.25. The heat evolved on combustion of 1 g starch (C6H10O5)n into CO2 and H2O(l) is 17.49 Kj/g. Compute the enthalpy of formation of 1 g starch. Given heat of formation for H2O(l) is -285.85 Kj/mole and that of CO2 is -293.7 Kj/mole.

26. Given the bond energy for H-H, O=O and O-H bonds are 104, 118 and 111 kcal/mol respectively. Calculate the heat of reaction

H2(g) + 1/2O2(g) H2O(g) 27. Calculate ∆Ho for the reaction

CO2(g) + H2(g) CO(g) + H2O(g) Given that ∆Hf

o for CO2(g), CO(g) and H2O(g) are -393.5, -111.31 and -241.8 kj/mol respectively.

28. Calculate ∆H for the reaction

CH2=CH2(g) + 3O2(g) 2CO2(g) + 2H2O(l) at 25oC.Given the bond energies in KJ/molC-H 416.2 O-H 464.4O=O 493.7 C=C 615

C=O 711.329. Determine ∆H of the reaction

C(s) + 2H2(g) CH4(g) from the following data:C + O2 CO2, ∆H = -393.7 kjH2 + 1/2O2 H2O, ∆H= -285.7 kjCH4 + 2O2 CO2 + 2H2O, ∆H= -890.3 kj

SOLID STATE1. At what glancing angle would the first order diffraction (110) plane of KCl be observed, using X-ray of wavelength 154pm? The dimension of the unit cell is 315pm.2. Calculate the distance between (100) planes of a crystal which exhibits first order reflection at an angle of incidence equal to 30 with X-rays of wavelength 2x10-10m.3. From the following data, design the crystal lattice possessed by a metal: atomic mass = 95.94amu, density = 10.2g/cc, cube edge length = 3.1468Å, Avogadro number = 6.02x1023mol-1.4. The unit cube length for LiCl is 5.14Å. Assuming anion-anion contact, calculate the ionic radius of the choride ion.5. NaCl has face-centered cubic structure. Its density is 2.163x10-3gm-3. What is the edge length of the unit cell? Molecular mass of NaCl = 58.45x10-3kg/mol.6. Calculate Avogadro number if the density of NaCl = 2.165g/cc, distance between Na+

and Cl- ions in NaCl crystal = 281pm.7. A body-centered cubic element of density 10.3g/cc has a cell-edge of 314pm. Calculate the atomic mass of the element.8. Sodium choride has a face-centered cubic crystal. What is the co-ordination number of Na?9. Calculate the number of atoms per unit cell of elementary crystalline solid with body-centered cubic lattice.10. When X-rays of wavelength 0.090nm are diffracted by a metallic crystal, the angle of first order diffraction (n=1) is measured to be 15.2 . What is the distance (in pm) between the layers of atoms responsible for diffraction?11. The distance between layers in a NaCl crystal is 282pm. X-rays are diffracted from these layers at an angle of 23 . Assuming n=1, calculate the wavelength of theX-rays in nm.12. Aluminium crystallizes in fcc structure. Calculate the molar mass of Al atoms, if length of unit cell is 404pm and density of aluminium is 2.7g/cc. 13. Chromium has monotonic body-centered cubic structure. Its edge is 300pm. What is its density? (molar mass of Cr= 52 g/mole, Avagadro number N= 6.023x1023 mol-1 13. The distance between layers in a NaCl crystal is 282pm. X-rays are diffracted from these layers of at an angle of 230. Assuming n=1, calculate the wavelength of the X-rays in nm.

14. The X-ray powder pattern of NaCl is taken with a chromium tube giving Cr Kα = 229.1 pm. The ϴ

values of the lines are: 20°36’, 23°58’, 35°4’, 42°21’, 44°43’, 54°20’, 62°17’, 65°16’. From these data determine the value of each dh k l and index the lines. From the hkl values, show that

this is a face-centered system.

15. The smallest observed diffraction angle of silver taken with Cu Kα radiation (λ = 154.18 pm)

is 19.176°. This angle is associated with the (111) plane in the cubic close-packed structure of silver.

(a.) Determine the value of the unit cell length a.

(b). If D(Ag) = 10.500 g cm-3 and M = 107.87 g mol-1, calculate the number of atoms in the unit cell. (10)

16. Explain the structure of NaCl, CsCl ?crystal formation. 17. Describe the structure of (i) Diamond (ii) Graphite (iii) Fullerene18. Sodium fluoride is known to form a cubic closed-packed structure. The smallest angle obtained with Cu Kα radiation (λ = 1.5418 Å) is 16.72° and is derived from the (111) planes.

Find the value of a, the unit cell parameter.

ELECTROCHEMISTRY

1. A zinc rod is placed in 0.1M zinc sulphate solution at 298 K. write the electrode reaction and calculate the electrode potential (Given that EO = -0.7 V)

2. At 25˚C, molar conductance of 0.002M HF is 176.2Ω-1cm2mol-1 and at infinite dilution is 405.2Ω-1cm2mol-1. What is the degree of dissociation of HF in 0.002M solution.3. The specific conductance of 0.01M solution of acetic acid was found to be 0.0163Sm -1 at 25˚C. Calculate the degree of dissociation of the acid. Molar conductance of CH 3COOH at infinite dilution is 390.7x10-4Sm2mol-1 at 25˚C.4. Can we use a copper vessel to store 1M AgNO3 solution. Given Eo

Cu2+/Cu = 0.34 V ; Eo

Ag+/Ag = 0.80 V5. The standard reduction potential of Cu2+/Cu and Ag+/ Ag electrodes are 0.337 V and 0.799 V respectively. Construct a galvanic cell using these electrodes so that its Eocell is positive. For what [Ag+] will the EMF of cell be zero if [Cu2+] is 0.01M. 6. Calculate the EMF of the following cell

Zn(s) / Zn2+(0.10 M) // Sn2+(0.001 M) / Sn(s) Eo

(Zn2+/Zn) = -0.76 VEo

(Sn2+/Sn) = -0.14 V7. Calculate the equilibrium constant for the reaction at 25oC

Zn / Zn2+ (0.01M) // Fe2+ (0.001M) / Fe3+ (0.01M) Given, Standard EMF of the cell = 1.71 V

8. A cell is formed by dipping Zn rod in 0.01 M Zn2+ solution and Ni rod in 0.5M Ni2+ solution. The standard electrode potential of Zn and Ni are 0.76 V and -0.25 V respectively. Write the cell representation, cell reaction and calculate the EMF of the cell.

9. Calculate the valency of mercurous ions with the help of the following cell:

Hg / 0.001 N mercurous nitrate in 0.1 N HNO3 // 0.01 N mercurous nitrate in 0.1 N HNO3

/ HgWhen the EMF observed at 18oC is 0.029 V .

10. The EMF of the cell Ag/ 0.0093 N AgNO3 // AgNO3 (x) / Ag is 0.086 V at 25oC. Fnd the concentration x.

11. Calculate the equilibrium constant for the Daniel cell at 25oC, if standard oxidation potential for Zn electrode is 0.765 V and for copper electrode is -0.337 V.

12. Calculate the half cell potential at 298 K for the reaction

Zn2+ + 2e- Zn (s), if [Zn2+] is 5M and EoZn2+ / Zn = -0.76 V

13. Calculate the equilibrium constant for the following reaction

Cu(s) + 2Ag+ Cu2+ + 2Ag Given, Eo

cell = 0.46 V

14. A conductivity cell on being filled with a 0.02M solution at 25 C showed a resistance of 165Ω. The specific conductance of KCl solution used is 2.77x10-3Ω-1cm-1. The same cell containing 0.01M NaCl solution gave an electrical resistance o 384Ω. Calculate the specific and equivalent conductance of NaCl solution.

15. Calculate the equilibrium constant for the cell at 25C Zn/Zn+2 (0.01M)//Cu+2 (.001M)/Cu, Given standard EMF of Cell = 1.10V

16. How does electrochemical series help in predicting whether a metal will react with the acid to give hydrogen gas or not.17. Define transport number of an electrolyte and explain any one method how it will be measured18. A solution containing 0.00739g of AgNO3 per gram of water was electrolyzed between silverelectrodes. During the experiment 0.0078g of silver was deposited in a silver coulometer placed in series. At the end of experiment, the anodic solution contains 23.14g of water and 0.236g of AgNO3.19. What are the transport number of Ag+ and NO3

- ions? (At. mass of Ag = 108, N = 14, O = 16)

20. In a moving boundary experiment 0.01 M HCl solution was treated on a lithium chloride solution. The tube used had a diameter of 1 cm. when a current of 11.0 milliampere was passed for 20 min., the H+ ions – Li+ ions boundary moved through 13.9 cm. Calculate the transport number of H+, Cl- ions in HCl solution used? (F = 96500 coulombs)

21. (a) The equivalent conductance of a 0.005 N NaOH solution is 240 mho cm2. What is the specific conductance and electrical resistance if the electrodes are 1 cm apart and each have a surface area of 1 cm2. (b) Om what factors does the conductance of a solution depend ? How would you proceed to

determine the conductivity of a solution?

22. Calculate the single electrode potential for copper metal in contact with 0.10M Cu+2 solution. E˚ for Cu is 0.34V. 23. Calculate EMF of the cell in which the reaction is, Mg(s)+ 2Ag+(aq) → Mg+2(aq) + 2Ag(s); Given; [Mg+2] = 0.130M and [Ag+] = 1.0x10-4M & E˚Ag+/Ag

= 0.80V and E˚Mg+2/Mg = -2.37V. 24. Calculate the EMF of the cell: ZnZn+2(1M) Ag+(1M)Ag ; Given; E˚Zn/Zn+2 = 0.762V and E˚Ag+/Ag = 0.800V.25. Predict whether the reaction, 2Ag(s)+Zn+2(aq)→2Ag+(aq)+ Zn(s) is feasible or not. Given; E˚Ag+/Ag

= 0.80V and E˚Zn+2/Zn = - 0.763V.26. Determine the feasibility of the reaction, 2Al(s) + 3Sn+4(aq) → 2Al+3 + 3Sn+2(aq); Given; E˚Al+3/Al

= -1.66V and E˚Sn+4/Sn+2 =+0.15V.27. What is the potential of a half cell consisting of Zn electrode in 0.01M ZnSO4 solution at 25˚C if E˚ for the cell is 0.763V.28. Calculate the EMF of the cell, ZnZn+2(0.001M) Ag+(0.1M)Ag; Given; E˚Ag+/Ag

= +0.80V and E˚Zn/Zn+2 = -0.76V. 29. The EMF of the following cell at 25˚C is 0.4450, Pt ; H2(1atm)H+(test sol) KCl salt sol Hg2Cl2 Hg. Calculate the pH of the unknown solution. Ecalomel = 0.2415V.30. Find the pH of a solution placed in a hydroquinone half-cell which was coupled with standard calomel electrode. The EMF of the combined cell was determined to be 0.123V at 25˚C. Ecalomel = 0.2415V and E˚Q = 0.6996V.31 . A Zn rod is placed in 0.1M solution of ZnSO4 at 25˚C. Assuming that the salt is dissociated to95% at this dilution, calculate the potential of the electrode at this temperature. Given; E˚(Zn+2/Zn) = -0.76V. 32. Consider the following cell, Cd Cd+2(1M) H+(aq)(1M) H2(g) Pt. Write down the overall reaction indicating the anodic and cathodic half reactions.33. Consider the reaction, 2Ag+ + Cd 2Ag + Cd+2 . Standard reduction potentials of Ag+/Ag and Cd+2/Cd couples are 0.80 and -0.40V, respectively. (i) What is the E˚ of this reaction? (ii) Which is negative electrode of the cell?34. The following reaction takes place in a cell, Zn(s) + Co+2 Co(s) + Zn+2 Write down the electrode reactions and calculate the standard EMF of cell. Given; E˚Zn/Zn+2 = 0.76V and E˚Co/Co+2 = 0.28V.35. What is the standard potential of a cell that uses the Zn+2/Zn and Ag+/Ag couples? Which couple is negative? Write the equation for the cell reaction occurring at unit relative concentration. The standard electrode potentials for Zn+2/Zn and Ag+/Ag are -0.763V and +0.779V, respectively.36. The standard reduction potentials of Cu+2/Cu and Ag+/Ag electrodes are 0.337 and 0.799V, respectively. Construct a galvanic cell using these electrodes so that its standard EMF is positive. For what concentration of Ag+ will the EMF of the cell at 25˚C be zero if the concentration of Cu+2 is 0.01M?37. EMF of a cell was found to be 0.1595V at 25˚C. Calculate the pH of acid solution. EMF of standard calomel and quinhydrone electrodes are +0.2440 and +0.6990V, respectively. 38. Write the cell reaction for Zn Zn+2(0.1N) Ag+(0.01N) Ag.

39. Calculate the standard EMF of Ni+2/Ni electrode if the cell potential of the cell NiNi+2(0.01M)Cu+2(0.1M)Cu is 0.59V. Given; E˚Cu+2/Cu = 0.34V.40. Calculate the standard EMF of the cell, Cr(s)Cr+3(aq)Ag+(aq)Ag(s); if E˚Cr/Cr+3 = +0.744V and E˚Ag/Ag+ = -0.80V.41. The specific conductance o water is 7.6x10-2Sm-1 and the specific conductance of 0.1M aqueous solution of KCl is 1.1639Sm-1. A cell has a resistance of 33.20Ω when filled with 0.1M KCl solution and 300Ω when filled with 0.1M CH3COOH solution. Calculate the molar conductance of acetic acid.

42. A conductivity cell filled with 0.1M solution of KCl at 25 C has a measured resistance of 24.96Ω. Calculate the cell constant if the specific conductance for 0.1M solution of KCl is 0.011639Ω-1cm-1 and that for conductivity water is 7.5x10-8Ω-1cm-1. When the cell is filled with a 0.01M solution of CH3COOH, the cell resistance is 1982Ω. Calculate the molar conductivity of CH3COOH at this concentration.

43. What will be the degree of ionization of N/1000 acetic acid solution if its equivalent conductance is 50mhos and the value of equivalent conductance at infinite dilution is 350mhos.44. At 25˚C, molar conductance of 0.01M aqueous solution of CH3COOH is 16.32x10-4Sm2

mol-1 and at infinite dilution is 390.72x10-4Sm2mol-1. Calculate degree of dissociation.45. At 25˚C, molar conductance of 0.002M HF is 176.2Ω-1cm2mol-1 and at infinite dilution is 405.2Ω-1cm2mol-1. What is the degree of dissociation of HF in 0.002M solution.46. The specific conductance of 0.01M solution of acetic acid was found to be 0.0163Sm -1 at 25˚C. Calculate the degree of dissociation of the acid. Molar conductance of CH 3COOH at infinite dilution is 390.7x10-4Sm2mol-1 at 25˚C.47. Can we use a copper vessel to store 1M AgNO3 solution. Given Eo

Cu2+/Cu = 0.34 V ;

EoAg+/Ag = 0.80 V

48. The standard reduction potential of Cu2+/Cu and Ag+/ Ag electrodes are 0.337 V and 0.799 V respectively. Construct a galvanic cell using these electrodes so that its Eocell is positive. For what [Ag+] will the EMF of cel be zero if [Cu2+] is 0.01M.

49. Calculate the EMF of the following cell. Determine the feasibility of the reaction, 2Al(s) + 3Sn+4(aq) → 2Al+3 + 3Sn+2(aq); Given; E˚Al+3/Al

= -1.66V and E˚Sn+4/Sn+2 =+0.15V.50 . A Zn rod is placed in 0.1M solution of ZnSO4 at 25˚C. Assuming that the salt is dissociated to95% at this dilution, calculate the potential of the electrode at this temperature. Given; E˚(Zn+2/Zn) = -0.76V.51. Write the cell reaction for the cell: Zn, Zn+2(1M) Fe+2(1M), Fe+3(1M); Pt. 12. Calculate the potential of the cell and write down the cell reaction: CoCo+2(0.01M) Pd+2(0.5M)Pd Given; E˚Co+2/Co = -0.28V and E˚Pd+2/Pd = 0.99V.

52. While determining the pH of a solution, the quinhydrone electrode, H+, Q, QH2 was used in conjunction with a saturated calomel electrode, Hg, Hg2Cl2(s); KCl(sat. sol) H+(unknown); Q,

QH2, Pt. The EMF of the cell was found to be 0.2640V at 25˚C. Calculate the pH of the solution at this temperature. Given; Ecalomel = +0.2422V at 25˚C and E˚(H+, Q, QH2) = +0.6996V.19. Calculate the equilibrium constant at 25˚C for the reaction, Zn(s) + Cu+2(1M) Cu(s) + Zn+2(1M). E˚ for this cell is 1.10V.

53. Consider the reaction, 2Ag+ + Cd 2Ag + Cd+2 . Standard reduction potentials of Ag+/Ag and Cd+2/Cd couples are 0.80 and -0.40V, respectively. (i) What is the E˚ of this reaction? (ii) Which is negative electrode of the cell?The specific conductance of a saturated solution of CaF2 at 18 C was found to be 4.25x10-3 Sm-1 and the specific conductance of water used for preparing the solution is 2 x 10-4 Sm-1. The molar ionic conductivities at infinite dilution of Ca+ and F- are 104.0 x 10-4 and 48 x 10-4 S m2mol-1, respectively. What is the solubility and solubility product of CaF2?

54. Calculate the solubility and solubility product of Co2[Fe(CN)6] in water at 25 C. Conductivity of a saturated solution of Co2[Fe(CN)6] is 2.06x10-6Ω-1cm-1 and that of water used is 4.1x10-7Ω-

1cm-1. The ionic molar conductivities of Co+2 and [Fe(CN)6]-4 are 86.0 and 444.0Ω-1cm2mol-1, respectively.

55. In a moving boundary experiment with 0.1N KCl using 0.065N LiCl as indicator solution, a constant current of 0.005893amp was passed for 2180 seconds and the boundary was observed to move through 5.60cm in a tube of 0.1142cm2 cross-section. Calculate the transport numbers of K+ and Cl- ions.56. A decinormal solution of AgNO3 was electrolysed between platinum electrodes. After passing a small current for two hours, a fall of concentration of 0.0005124 gram equivalents occurred in the anodic solution. The mass of copper deposited in a copper coulometer placed in series was found to be 0.03879g. Calculate the transport numbers of Ag+ and NO3

- ions in AgNO3. (E.W. of Cu = 31.8).57. A solution of AgNO3 was electrolysed between silver electrodes. Before electrolysis, 10g of the solution contained 0.01788g of AgNO3. After the experiment, 20.09g of the anodic solution contained 0.06227g of AgNO3. At the same time, 0.009479g of copper was deposited in the copper coulometer placed in series. Calculate the transport numbers of Ag+ and NO3

- ions. (Ag = 108 and Cu = 63.6). 58. A AgNo3 solution containing 0.00739g of AgNO3 per gram of solution is electrolysed between Ag electrodes. During the experiment, 0.078g of silver is deposited at the cathode. At the end of the experiment, anode contains 23.14g of solution containing 0.236g of AgNO3. What are the transport numbers of Ag+ and NO3

- ions?59. A solution of AgNO3 containing 0.0074g AgNO3 per gram of solution was electrolysed using silver electrodes. During the experiment, 0.0785g of silver was deposited in a silver voltameter. At the end of electrolysis, 25g of anode solution contained 0.2553g of AgNO3. Calculate transport number of NO3

- ion.

CORROSION

1. Describe the theories related to the corrosion such as Dry Theory, Wet Theory and Acid Theory. 2. Give reasons: (i) A part of iron nail inside the wood undergoes corrosion easily.(ii) A part of the ship inside water undergoes corrosion(iii) Corrosion of water filled steel tanks occurs below the water line.(iv) Rusting of iron is quicker in saline water than in ordinary water.

3. Explain the most cost effective method to prevent corrosion of large buildings.

4. How relative area of cathode & anode affects the rate of corrosion

5. Pitting corrosion is autocatalytic, self stimulating and self propagating. Explain.6. Write short notes on the following:

(a) Electroplating(b) Impressed current cathodic protection

ORGANIC CHEMISTRY

1. Explain the following reaction:

2.

Compound ‘A’ C6H14O on dehydration gives an alkene ‘B’ C6H12. Alkene ‘B’ on ozonolysis gives ‘C’ and ‘D’. ‘C’ does not react with alkaline KMnO4, while ‘D’ gives corresponding acid. What will be the structure of ‘A’, ‘B’, ‘C’ and ‘D’? Write the complete chemical reaction. What will be the isomeric form of ‘A’ which can give the same results?

3. Complete the following reaction with mechanism:

4. Write the mechanism of the following reaction:

5.

Explain why:

a. Haloalkanes undergo nucleophilic substitution reactions whereas haloarenes undergo electrophilic substitution. Account for it.

b. The treatment of alkyl chloride with aqueous KOH leads to formation of alcohols whereas in the presence of alcoholic KOH, alkenes are formed as the major product. Explain why.

6. With reason, arrange the following in increasing order of acidity : phenol, p-methyl phenol, m-nitrophenol and p-nitrophenol .

7. Give the detail mechanism for the following conversion

Benzene to AnilineBenzene to Styrene

8. What would happen if we dissolved an aldehyde in an alcohol and acid, instead of water?Explain the mechanism of acetaldehyde interaction.

9. Predict the products of the following reactions.

10. Identify the starting material that would give the following product.

CHEMICAL KINETICSQ1. In a reaction 2A P, the concentration decreases from 0.5 mol/lt to 0.4 mol/lt in 10

min calculate the rate during this interval.Q2. For a reaction 3A P, it is found that the reaction of rate doubles if concentration of

A is increased four times. Calculate order of reaction.Q3. Calculate the order of a reaction for which the rate becomes half if volume of container

having same amount of reactant is doubled.Q4. What will be the intial rate of reaction if the rate constant is 10 -3 min-1 and the

concentration of reactant is 0.2 mol/dm3? How much of the reactant will be converted into product in 200 minutes?

Q5. The rate of change of concentration of C in the reaction 2A+ B 2C +3 D was reported as 1 mol/lt/sec. Calculate the reaction rate as well as rate of change of concentration of A , B and D.

Q6. In first order reaction 25% decomposition requires 40.4 minutes. Calculate the rate constant.

Q7. 75% of a reaction of first order was completed in 72 min. When was it half completed?Q8. A first order reaction is 25% completed in 30 minutes. Calculate (i) rate constant (ii) Half

life (iii) time required for 75 % conversion to be completed.Q9. 50 % of first order reaction is completed in 231 minutes. Calculate the time required to

complete 90 % of the reaction.Q10. Rate constant for first order reaction is 2.31 X 10-3 . Calculate its half life time.Q11. Derive the rate constant for the consecutive first-order reaction of type

A k1 B k2 C; using steady state approximation.Calculate order w.r.t individual reactant, write the arte expression for reaction, calculate the rate

constant? What will be the initial rate fo reaction if [NO] =[H2] = 8.0 X 10 -3 mol/ dm3.Q12 The half life for first order reaction is 2.5 X 10 3

. How long wil it take for 1/5 th of the reaction to be left behind.

Q13. If a unimolecular reaction is one quarter completed in 100 min. What is specific rate constant K and period of half time.

Q14. Benzene diazonium chloride decomposes in the presence of H2O according to the first order kinetic. If the velocity constant at 25 0 C is 2.8 X 10-3 min-, and the activation energy is 11.9 Kcal/mol. Find the velocity constant at 35 0 C

Q15. Show that for first order reaction the time required for 99.9 % completion is 10 times required for 50 % completion.

Q16. A second order reaction where a= b, is completed in 500 sec. How long will it take for the reaction to go to 60 % completion?

Q17 Half life of first order reaction is 5 minutes. What will be the concentration of reactant after 30 minutes if initial concentration is 128 mol/lt.?

Q18. A reaction proceeds 5times more at 600 C as it does at 30 0C. Calculate the energy of activation.

Q19 A Ist order reaction is 50 % completed in 30 min at 270 C and in 10 min at 470 C. Calculate (a) the rate constant at 270 C and 470 C (b) Energy of activation.

Q20 The following mechanism have been suggested or the reaction H2 + I2 2HI at 4000 C

a) H2 + I2 2HI

b) I2 2I, 2I + H2 2HI (slow)

c) I2 2I, I + H2 IH2 , IH2 + I (slow) 2HI

Q21 How many times the rate of reaction increases at 20°C for a reaction having the activation energies in the presence and absence of a catalyst as 50 kJ/mol and 75 kJ/mol.

Q22. A certain substance R1 is mixed with an equal moles of another substance R2. At the end of 30 seconds, R1 is 25% reacted. How much will R1 and R2 be left unreacted at the end of 35 seconds, if the reaction is: (a) first order in R1 and independent of R2: (b) first order in both R1 and R2.

Q23. The following mechanism has been suggested for the thermal decomposition of NO2

Overall reaction: 2NO2 2NO + O2

Mechanism:NO2 + NO2 NO + NO + O2

NO2 + NO2 NO3 + NO

NO3 + NO 2NO2

NO3 + NO2 NO + NO2 + O2

Find the rate of reaction in terms of NO2.

Q24. Discuss the effect of pressure and temperature on the reaction rate.Q25. How half life of nth order & zero order reaction will change with change in concentration.

Q26. For the formation of HBr

H2 + Br2 2HBr

The following mechanism has been proposed

find the reaction rate in terms of HBr.

Q27. Half life of first order reaction is 5 minutes. What will be the concentration of reactant after 30 minutes if initial concentration is 128 mol/lt.?

K1

K2

K3

K4

Q28. A reaction proceeds 5times more at 600 C as it does at 30 0C. Calculate the energy of activation. Q29. A Ist order reaction is 50 % completed in 30 min at 270 C and in 10 min at 470 C. Calculate (a) the rate constant at 270 C and 470 C (b) Energy of activation.

Q30. Explain the rate of the reaction for the following reactions using Lindemann mechanism and predict the rate constants

POLYMERS1. Give reason:

I. Aliphatic polyesters are not of much industrial importance.II. Bakelite can be stored for indefinite period of time.

III. Polypropylene has less oxidation stability than Polyethylene.IV. Butadiene is copolymerized with styrene.V. Suspension polymerization is known as bead polymerization

2. Give preparation, properties and applications of any two aliphatic polyamides3. Give the structure of monomer for the given polymers: PMMA, PET.Explain 4. Why HDPE is 90% crystalline while LDPE have 40% crystalline structure

3. Solution polymerization is used to synthesis polymers having final application in liquid form

6. A monomer “D” is insoluble is water, explain the polymerization technique that you will suggest.7. Compare the following with suitable examples:

(a) Thermosetting & Thermoplastic polymers(b) Addition & Condensation Polymerizaion

8. What is copolymerization? Write the preparation, properties and uses of Teflon and poly ethylene. (5)

9. (a) Why natural rubber needs compounding? (b) What are elastomers and how do they differ from natural rubber?

10. Explain the following addition polymerization techniques: (a) Solution polymerization (b) Emulsion polymerization

11. Explain the following polymers brief synthesis, properties and applications (a) polyurethane , (b) PAN , (c) Polymethylmethacrylate (PMMA), (d) Resins (phenol-formaldehyde)

NANOCHEMISTRY1. Discuss how optical property and surface energy get affected as we move from macro to nano scale. 2. Give any two methods for the synthesis of nano particles.4. Explain the synthesis of silica nanoparticles by microemulsion technique, how this technique is more advantage in the synthesi s of inorganic nanomaterials than other methods?

5. Describe the preparation of Carbon Nano Tubes (CNTs) by plasma enhanced chemical vapour deposition(PECVD) technique, how this method is better than Thermal CVD ?

6. ZnO nanoparticles are used as better photocatalysts in chemical catalysis why? Explain the few applications of nanoparticles in chemical catalysis.

7. Using Sol-Gel technique one can easily synthsize metal oxide (MO)nanoparticles, explain the synthsis of MO using Hydrothermal method.