Chemistry - B.Tech 2nd Semester Special Exam., 2020

2020Semester 2Civil-CAEnd Semester
Bihar Engineering University, Patna
B.Tech 2nd Semester Special Exam., 2020

Chemistry

Time: 3 hoursCode: 100103/100203Full Marks: 70

Instructions:

  1. The marks are indicated in the right-hand margin.
  2. There are NINE questions in this paper.
  3. Attempt FIVE questions in all.
  4. Question No. I is compulsory.
Q.1 Answer any seven questions in brief:[2x7=14]
  1. Arrange the following in increasing order of stability:

    \( \text{N}_2, \text{N}_2^+, \text{N}_2^-, \text{N}_2^{2-} \)

  2. Transition metal ions like \( \text{Cu}^+ \) and \( \text{Ag}^+ \) are colourless. Why?

  3. Which of \( \text{Cr}^+ \) or \( \text{Cu}^+ \) is expected to be coloured?

  4. \( ^{13}\text{C} \) is NMR active, but \( ^{12}\text{C} \) is not. Why?

  5. What is the direction of a reaction when \( \Delta G = 0 \)?

  6. Why is work not a state function?

  7. Write the relationship between parts per million [ppm] and Clarke's degree [°C].

  8. What is critical temperature of a gas?

  9. Arrange the following ligands in order of increasing field strength:

    \( \text{CN}^-, \text{CO}, \text{H}_2\text{O}, \text{NH}_3 \)

  10. Arrange the following in order of their increasing reactivity in nucleophilic substitution reaction:

    \( \text{CH}_3\text{F}, \text{CH}_3\text{I}, \text{CH}_3\text{Br}, \text{CH}_3\text{Cl} \)

Q.2 Solve all parts :[4+4+6=14]
  1. At what temperature will water boil when the applied pressure is 528 mm of Hg? (Latent heat of vaporisation of water = 545.5 cal/g)

  2. At NTP, 2.8 L of \( \text{O}_2 \) were mixed with 19.6 L of \( \text{H}_2 \). Calculate the increase in entropy (assume ideal gas behaviour).

  3. The equilibrium constants for the reaction \( \text{H}_2[g] + \text{S(s)} \rightarrow \text{H}_2\text{S[g]} \) are 18.5 at 925 K and 9.25 at 1000 K. Calculate standard enthalpy of the reaction. Also calculate \( \Delta G^\circ \) and \( \Delta S^\circ \) at 925 K.

Q.3 Solve all parts :[4+5+5=14]
  1. The uncertainties in the position and velocity of a particle are \( 9.5 \times 10^{-10} \, \text{m} \) and \( 5.5 \times 10^{-20} \, \text{ms}^{-1} \), respectively. Calculate the mass of the particle. \( (h = 6.626 \times 10^{-34} \, \text{J·s}) \)

  2. Calculate the kinetic energy of a moving electron which has a wavelength of 48 pm. [Mass of electron = \( 9.11 \times 10^{-31} \, \text{kg} \)]

  3. Discuss the failures of classical mechanics to explain properties of particles at atomic and sub-atomic levels.

Q.4 Solve both questions :[8+6=14]
  1. Draw the MO energy-level diagram for \( \text{O}_2 \) and based on the diagram, and explain the magnetic property observed in \( \text{O}_2 \), \( \text{O}_2^+ \) and \( \text{O}_2^- \).

  2. Explain geometrical isomerism and optical isomerism for transition metal complex with an example for each.

Q.5 Solve all parts :[4+4+6=14]
  1. The internuclear distance of NaCl is \( 2.36 \times 10^{-10} \, \text{m} \). Calculate the reduced mass and moment of inertia of NaCl. (Atomic mass of Cl = \( 35 \times 10^{-3} \, \text{kg mol}^{-1} \) and Na = \( 23 \times 10^{-3} \, \text{kg mol}^{-1} \))

  2. Calculate the force constant for CO, if it absorbs at \( 2.143 \times 10^{5} \, \text{m}^{-1} \). (Atomic mass of C = \( 12 \times 10^{-3} \, \text{kg mol}^{-1} \) and O = \( 16 \times 10^{-3} \, \text{kg mol}^{-1} \))

  3. How many \( ^{1}\text{H} \) NMR signals are there in—

    1. \( \text{CH}_3-\text{CH}_3 \)
    2. \( \text{CH}_3-\text{CH}_2-\text{CH}_3 \)
    3. \( \text{CH}_3-\text{CH}_2-\text{Cl} \)
    4. \( \text{CH}_3-\text{CHCl}-\text{CH}_3 \)
    5. \( \text{C}_6\text{H}_5\text{CH}_3 \)
    6. \( \text{C}_6\text{H}_5\text{CH}_2\text{CH}_3 \)
Q.6 Solve both questions :[5+9=14]
  1. 2 mole of \( \text{NH}_3 \) at 300 K occupy a volume of \( 5 \times 10^{-3} \, \text{m}^3 \). Calculate the pressure using van der Waals equation \( (a = 0.417 \, \text{N m}^4 \, \text{mol}^{-2} \) and \( b = 0.037 \times 10^{-3} \, \text{m}^3 \, \text{mol}^{-1}) \). Compare the above result with the pressure calculated using ideal gas equation.

  2. Write short notes on the following:

    1. Magnetic resonance imaging
    2. Fingerprint region in infrared spectroscopy
    3. Different types of electronic excitations
Q.7 Solve both questions :[7+7=14]
  1. Consider the following half-cell reactions:

    \( \text{PbO}_2(s) + 4 \text{H}^+ (aq) + \text{SO}_4^{2-} (aq) + 2e \rightarrow \)
    \( \text{PbSO}_4(s) + 2\text{H}_2\text{O}, E^\circ = 1.70 \, \text{V} \)

    \( \text{PbSO}_4(s) + 2e \rightarrow \text{Pb}(s) + \text{SO}_4^{2-} (aq) \), \( E^\circ = -0.31 \, \text{V} \)

    Write the cell (in proper cell notation) and the cell reaction. Calculate the value of \( E^\circ \) for the cell and the EMF generated if \( [\text{H}^+] = 0.1 \, \text{M} \) and \( [\text{SO}_4^{2-}] = 2 \, \text{M} \).

  2. A water sample had the following constituents per litre:

    \( \text{CaCO}_3 = 81 \, \text{mg} \), \( \text{MgHCO}_3 = 75 \, \text{mg} \), \( \text{CaSO}_4 = 136 \, \text{mg} \), \( \text{MgSO}_4 = 120 \, \text{mg} \), \( \text{NaCl} = 47 \, \text{mg} \)

    Calculate the quantity of temporary and permanent hardness in the water sample. Calculate the quantity of lime (78% purity) and soda (92% purity) required for softening of 1.5 million litres of the above water sample.

Q.8 Solve all parts :[4+5+5=14]
  1. Describe two methods used for resolving racemic mixtures into optically active compounds.

  2. Write the possible optical isomers of tartaric acid and indicate the point of symmetry or plane of symmetry (if any) in the isomers.

  3. Differentiate between (i) enantiomers and diastereomers and (ii) racemic mixture and meso compounds.

Q.9 Solve all parts :[4+4+6=14]
  1. How do you decide whether the reaction \( \text{CH}_3\text{Br} + \text{OH}^- \rightleftharpoons \text{CH}_3\text{OH} + \text{Br}^- \) proceeds by \( S_N1 \) or \( S_N2 \) reaction? Give justification in favour of your answer.

  2. Draw the energy profile diagram for the following reaction:

    \( (\text{CH}_3)_2\text{CBr} + \text{OH}^- \rightleftharpoons (\text{CH}_3)_2\text{COH} + \text{Br}^- \)

  3. Write short notes on the following:

    1. Steric effects
    2. Diels-Alder reaction