3.10 In a reaction between A and B, the initial rate of reaction (r0) was measured for different initial concentrations of A and B as given below: A/ mol L–1 0.20 0.20 0.40 B/ mol L–1 0.30 0.10 0.05 r0/mol L–1s–1 5.07 × 10–5 5.07 × 10–5 1.43 × 10–4 What is the order of the reaction with respect to A and B? 3.11 The following results have been obtained during the kinetic studies of the reaction: 2A + B ® C + D Experiment [A]/mol L–1 [B]/mol L–1 Initial rate of formation of D/mol L–1 min–1 I 0.1 0.1 6.0 × 10–3 II 0.3 0.2 7.2 × 10–2 III 0.3 0.4 2.88 × 10–1 IV 0.4 0.1 2.40 × 10–2 Determine the rate law and the rate constant for the reaction. 3.12 The reaction between A and B is first order with respect to A and zero order with respect to B. Fill in the blanks in the following table: Experiment [A]/ mol L–1 [B]/ mol L–1 Initial rate/ mol L–1 min–1 I 0.1 0.1 2.0 × 10–2 II – 0.2 4.0 × 10–2 III 0.4 0.4 – IV – 0.2 2.0 × 10–2 3.13 Calculate the half-life of a first order reaction from their rate constants given below: (i) 200 s–1 (ii) 2 min–1 (iii) 4 years–1 3.14 The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood had only 80% of the 14C found in a living tree. Estimate the age of the sample. 3.15 The experimental data for decomposition of N2O5 [2N2O5 ® 4NO2 + O2] in gas phase at 318K are given below: t/s 0 400 800 1200 1600 2000 2400 2800 3200 102 × [N2O5]/ 1.63 1.36 1.14 0.93 0.78 0.64 0.53 0.43 0.35 mol L–1 (i) Plot [N2O5] against t. (ii) Find the half-life period for the reaction. (iii) Draw a graph between log[N2O5] and t. (iv) What is the rate law ? Chemistry 86 Reprint 2025-26 (v) Calculate the rate constant. (vi) Calculate the half-life period from k and compare it with (ii).

1.5 A solution of glucose in water is labelled as 10% w/w, what would be the molality and mole fraction of each component in the solution? If the density of solution is 1.2 g mL–1, then what shall be the molarity of the solution? 1.6 How many mL of 0.1 M HCl are required to react completely with 1 g mixture of Na2CO3 and NaHCO3 containing equimolar amounts of both? 1.7 A solution is obtained by mixing 300 g of 25% solution and 400 g of 40% solution by mass. Calculate the mass percentage of the resulting solution. 1.8 An antifreeze solution is prepared from 222.6 g of ethylene glycol (C2H6O2) and 200 g of water. Calculate the molality of the solution. If the density of the solution is 1.072 g mL–1, then what shall be the molarity of the solution? 1.9 A sample of drinking water was found to be severely contaminated with chloroform (CHCl3) supposed to be a carcinogen. The level of contamination was 15 ppm (by mass): (i) express this in percent by mass (ii) determine the molality of chloroform in the water sample. 1.10 What role does the molecular interaction play in a solution of alcohol and water? 1.11 Why do gases always tend to be less soluble in liquids as the temperature is raised? 1.12 State Henry’s law and mention some important applications. 1.13 The partial pressure of ethane over a solution containing 6.56 × 10–3 g of ethane is 1 bar. If the solution contains 5.00 × 10–2 g of ethane, then what shall be the partial pressure of the gas? 1.14 What is meant by positive and negative deviations from Raoult's law and how is the sign of DmixH related to positive and negative deviations from Raoult's law? 1.15 An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the normal boiling point of the solvent. What is the molar mass of the solute? 1.16 Heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two liquid components are 105.2 kPa and 46.8 kPa respectively. What will be the vapour pressure of a mixture of 26.0 g of heptane and 35 g of octane? 1.17 The vapour pressure of water is 12.3 kPa at 300 K. Calculate vapour pressure of 1 molal solution of a non-volatile solute in it. 1.18 Calculate the mass of a non-volatile solute (molar mass 40 g mol–1) which should be dissolved in 114 g octane to reduce its vapour pressure to 80%. 1.19 A solution containing 30 g of non-volatile solute exactly in 90 g of water has a vapour pressure of 2.8 kPa at 298 K. Further, 18 g of water is then added to the solution and the new vapour pressure becomes 2.9 kPa at 298 K. Calculate: (i) molar mass of the solute (ii) vapour pressure of water at 298 K. 1.20 A 5% solution (by mass) of cane sugar in water has freezing point of 271K. Calculate the freezing point of 5% glucose in water if freezing point of pure water is 273.15 K. 1.21 Two elements A and B form compounds having formula AB2 and AB4. When dissolved in 20 g of benzene (C6H6), 1 g of AB2 lowers the freezing point by 2.3 K whereas 1.0 g of AB4 lowers it by 1.3 K. The molar depression constant for benzene is 5.1 K kg mol–1. Calculate atomic masses of A and B. Chemistry 28 Reprint 2025-26 1.22 At 300 K, 36 g of glucose present in a litre of its solution has an osmotic pressure of 4.98 bar. If the osmotic pressure of the solution is 1.52 bars at the same temperature, what would be its concentration?

5.15 Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: (i) [Fe(CN)6] 4– (ii) [FeF6] 3– (iii) [Co(C2O4)3]3– (iv) [CoF6] 3–