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Atkins & de Paula: Elements of Physical Chemistry 5e
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For the recombination of two methyl, CH3, radicals2 CH3 → C2H6the rate constants for the forward and backward reactions have been measured to be kr = 2.58 × 1013 mol-1 cm3 s-1 and kr′ = 5.36 × 10-4 s-1 respectively at a temperature of 1000 K. Calculate the equilibrium constant at this temperature. Remember that for a gas-phase reaction such as this, it will be necessary to express the concentrations in terms of the partial pressures of the various species.
The hydrolysis of t-bromobutane, C4H9Br, by hydroxide, OH-, ions in aqueous solution follows an SN1 reaction mechanism in which the rate-determining step is the loss of a bromide, Br-, ion, followed by rapid reaction with hydroxide ions. Which of the following rate laws is consistent with this mechanism?
The rate law for the multistep chain reaction H2 + Br2 → 2 HBr is Which of the following expresses the rate law in the limit of high pressures of bromine, Br2?
The kinetics of many radical-radical recombination reactions are diffusion controlled. Calculate the rate constant for a diffusion-controlled bimolecular reaction in water at 77°C. The viscosity of water at this temperature is η = 6.90 × 10-4 kg m-1 s-1.
The concentration gradient of ferrocene molecules in an aqueous ethanol solution in an electrochemical cell at 25°C is 1.2 mmol dm-3 cm-1. Calculate the magnitude of the flux of ferrocene molecules towards the electrode, given that the coefficient for diffusion of ferrocene in a dilute aqueous ethanol solution is 6.0 × 10-10 m2 s-1.
The diffusion coefficient for a dextrose molecule in water is 2.26 × 10-9 m2 s-1 at a temperature of 298.15 K. How far does an individual dextrose molecule travel in 1.00 s?
The diffusion coefficient for diffusion of collagen through water at 20°C has been measured to be 0.069 × 10-10 m2 s-1. Use the Einstein relation to calculate the effective radius of a collagen molecule, given that the viscosity of water at this temperature is 8.9 × 10-4 kg m-1 s-1.
The table below shows how, for the myosin-catalysed hydrolysis of ATP, the rate of reaction varies with substrate concentration. By constructing a Lineweaver-Burk plot, determine the value of the Michaelis constant.
The isomerization of cis- to trans-but-2-ene, C4H8, follows a Lindemann mechanism. At high pressure, the pseudo first-order rate constant for the isomerisation is 2 × 10-5 s-1 at 500°C. Given that, at this temperature, collisional activation occurs with an efficiency that is 1011 times slower than that of collisional deactivation, determine the rate constant for the final step of the mechanism.
The thermal decomposition of acetone, (CH3)2CO, proceeds via the formation of the stable intermediate ketene, CH2CO(CH3)2CO →CH2CO + CH4CH2CO → ½C2H4 + COThe rate constant for the initial decomposition of acetone is ka = 5.25 × 10-3 s-1, whilst the rate constant for the subsequent decomposition of ketene is kb = 15.23 × 10-3 s-1, at a temperature of 600°C. Calculate the time after which the ketene intermediate has reached its maximum concentration.
