P18C.2 The rates of thermal decomposition of a variety of cis- and trans-azoalkanes have been measured over a range of temperatures in order tosettle a controversy concerning the mechanism of the reaction. In ethanol anunstable cis-azoalkane decomposed at a rate that was followed by observingthe N, evolution, and this led to the rate constants listed below (P.S. Engeland D.J. Bishop, J. Amer. Chem. Soc. 97, 6754 (1975)). Calculate the enthalpy,entropy, energy, and Gibbs energy of activation at -20 °C.-24.82-20.73-17.02-13.00-8.9510ʻ x k/5"14.31.222.314.398.50

A unimolecular reaction is a reaction in which only one reactant molecule participates in the…

Answered: P18C.2 The rates of thermal…

Chemistry: The Molecular Science

5th Edition

ISBN:9781285199047

Author:John W. Moore, Conrad L. Stanitski

Publisher:John W. Moore, Conrad L. Stanitski

Chapter11: Chemical Kinetics: Rates Of Reactions

Section: Chapter Questions

Problem 83QRT

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The rate law for the hydrogenation (H) of ethylene (E) to form ethane (A) over a cobalt-molybdenum catalyst [Collection Czech. Chem. Commun.,51, 2760 (1988)] is (a)Suggest a mechanism and rate-limiting step consistent with the above rate law.(b)What was the most difficult part in finding the mechanism?
A solution of 100 g / L of acrylamide in methanol is polymerized at 25 ° C with 0.1 mol / Lof isobutyryl peroxide whose half-life is 9.0 h at this temperature and the efficiency inmethanol is 0.3. For acrylamide, kp2 / kt = 22 L / mol * s at 25 ° C and the termination is onlyby coupling. (a) What is the rate of polymerization, Rp? (b) How much polymer ishave you prepared in the first 10 minutes of reaction in 1 L of solution?
The value of ΔS° for the catalytic hydrogenation of acetylene to ethane, C2H2 (g) + 2H2 (g) → C2H6 (g) is __________ J/K∙ mol. A) -76.0 B) +440.9 C) -232.5 D) +232.5 E) +28.7
R. Atkinson (J. Phys. Chem. Ref. Data 26, 215 (1997)) has reviewed a large set of rate constants relevant to the atmospheric chemistry of volatile organic compounds. The recommended rate constant for the bimolecular reaction of O2 with an alkyl radical R at 298 K is 4.7 × 109 dm3 mol−1 s−1 for R = C2H5 and 8.4 × 109 dm3 mol−1 s−1 for R = cyclohexyl. Assuming no energy barrier, compute the steric factor, P, for each reaction. Hint: Obtain collision diameters from collision cross-sections of similar molecules in the Resource section.
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The diameter of the methyl radical is about 308 pm. What is the maximum rate constant in the expression d[C2H6]/dt = kr[CH3]2 for second-order recombination of radicals at 298 K? It is reported that 10 per cent of a sample of ethane of volume 1.0 dm3 at 298 K and 100 kPa is dissociated into methyl radicals. What is the minimum time for 90 per cent recombination?
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Distinguish between kinetic and the rmodynamic control of a reaction. Suggest criteria for expecting one rather than the other.
5.9. In the polymerization of H2N(CH2 )10 COOH to form nylon-11, what is the molecular weight of the species that has the largest weight fraction in the reaction mixture at 99% conversion ? [Ans. 18,300]
Consider the following complex mechansim: A + B → C + D with rate constant k1 C + D → A + B with rate constant k-1 C → B with rate constant k2 D → A with rate constant k3 A → D with rate constant k-3 Write down expressions for d[A]/dt, d[B]/dt, d[C]/dt, and d[D]/dt
Polypeptides are polymers of amino acids. Suppose that a long polypeptide chain can undergo a transition from a helical conformation to a random coil. Consider a mechanism for a helix–coil transition that begins in the middle of the chain:hhhh…⇌ hchh… hchh… ⇌ cccc… in which h and c label, respectively, an amino acid in a helical or coil part of the chain. The first conversion from h to c, also called a nucleation step, is relatively slow, so neither step may be rate determining. (a) Set up the rate equations for this mechanism. (b) Apply the steady-state approximation and show that, under these circumstances, the mechanism is equivalent to hhhh… ⇌ cccc….

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