Spectroscopy Drago book, second edition, chapter 9 electron paramagnetic resonance, page 402 ques 5 arper & RoW, New York, 1963.C. P. Shchter, Principles of Magnelic ResoR. M. Golding, “Applied Wave Mechanics," Van Nostrand Reinhold, New York 1964.A. Abragam, "The Principles of Nuclear Magnetism," Clarendon Press, Oxford, 1961.G. E. Pake and T. L. Estle, “Paramagnetic Resonance," 2nd e., W. A. Benjamin, NewYork, 1973.H. Fisher, "Magnetic Properties of Free Radicals," Landolt-Bernstein Tables, New SeriesGroup II, Vol. I, Springer-Verlag, Berlin, 1965.1. Convert the derivative curves below to absorption curves:EXERCISES(A)(B)2. a. How many hyperfine peaks would be expected from delocalization of the oddelectron in dibenzene chromium cation onto the rings?b. Using a procedure similar to that in Fig. 9–6, explain how the number of peaksarises and what the relative intensities would be.* For references heavily oriented toward the epr of transition metal ions, sec Chapter 13.402Chapter 9 Electron Paramagnetic Resonance Spectroscopy3. a. Copper(II) acetate is a dimer, and the two copper atoms are strongly interacting.The epr spectrum consists of seven lines with intensity ratios 1:2:3:4:3:2:1.Copper nuclei have an I value of ,, and copper acetate consists of a ground statethat is a singlet and an excited state that is a triplet. Explain the number and relativeintensity of the lines in the spectrum. [For answer, see B. Bleaney and K. D. Bowers,Proc. Roy. Soc. (London), A214, 451 (1952).]b. What would you expect to happen to the signal intensity as a sample of copperacetate is cooled? Why?4. Predict the epr spectrum for (SO3)2NO²-.H5. The mono negative ionO--0-can be prepared.HНa. How many lines are expected in the spectrum, and what would be the relativeintensities of these?b. What evidence would you employ and what experiments could be carried out toindicate electron delocalization onto the oxygen?c. The magnitude of ay in this material is 2.37 gauss. Compare the spin density onhydrogen in this molecule with that on a hydrogen atom.d. How would the sign of the proton hyperfine coupling constant indicate whetherthe odd electron was in a sigma- or pi-molecular orbital?e. Using the value of a, given above and the fact that the unpaired electron is in theT-system, calculate the spin density on the nearest neighbor carbon.6. The 1'C hyperfine coupling in the methyl radical is 41 gauss, and the proton hyperfinecoupling is 23 gauss. Sketch the spectrum expected for 13.CH, radical. [For answer,scc T. Cole et al., Mol. Phys., 1, 406 (1958).]7. Assume that all hyperfine lines can be resolved and sketch the spectrum for thechlorobenzene anion radical.8. Assuming all other factors constant, would line broadening be greater for a bimolecularprocess with a rate constant of 107 or with a rate constant of 1010?9. How many lines would you expect in the epr spectrum of (CN),CoO,Co(NH,),?Explain.10. The spectrum below is obtained for the NH,radical:a. Convert it to an absorption spectrum.b. How could you determine whether the larger or smaller splitting is due to hydrogen?c. Assume that the larger splitting is due to nitrogen. Construct a diagram similar toFig. 9–10 to explain the spectrum.

Question

Spectroscopy Drago book, second edition, chapter 9 electron paramagnetic resonance, page 402 ques 5 arper & RoW, New York, 1963.C. P. Shchter, Principles of Magnelic ResoR. M. Golding, “Applied Wave Mechanics,&#34; Van Nostrand Reinhold, New York 1964.A. Abragam, &#34;The Principles of Nuclear Magnetism,&#34; Clarendon Press, Oxford, 1961.G. E. Pake and T. L. Estle, “Paramagnetic Resonance,&#34; 2nd e., W. A. Benjamin, NewYork, 1973.H. Fisher, &#34;Magnetic Properties of Free Radicals,&#34; Landolt-Bernstein Tables, New SeriesGroup II, Vol. I, Springer-Verlag, Berlin, 1965.1. Convert the derivative curves below to absorption curves:EXERCISES(A)(B)2. a. How many hyperfine peaks would be expected from delocalization of the oddelectron in dibenzene chromium cation onto the rings?b. Using a procedure similar to that in Fig. 9–6, explain how the number of peaksarises and what the relative intensities would be.* For references heavily oriented toward the epr of transition metal ions, sec Chapter 13.402Chapter 9 Electron Paramagnetic Resonance Spectroscopy3. a. Copper(II) acetate is a dimer, and the two copper atoms are strongly interacting.The epr spectrum consists of seven lines with intensity ratios 1:2:3:4:3:2:1.Copper nuclei have an I value of ,, and copper acetate consists of a ground statethat is a singlet and an excited state that is a triplet. Explain the number and relativeintensity of the lines in the spectrum. [For answer, see B. Bleaney and K. D. Bowers,Proc. Roy. Soc. (London), A214, 451 (1952).]b. What would you expect to happen to the signal intensity as a sample of copperacetate is cooled? Why?4. Predict the epr spectrum for (SO3)2NO²-.H5. The mono negative ionO--0-can be prepared.HНa. How many lines are expected in the spectrum, and what would be the relativeintensities of these?b. What evidence would you employ and what experiments could be carried out toindicate electron delocalization onto the oxygen?c. The magnitude of ay in this material is 2.37 gauss. Compare the spin density onhydrogen in this molecule with that on a hydrogen atom.d. How would the sign of the proton hyperfine coupling constant indicate whetherthe odd electron was in a sigma- or pi-molecular orbital?e. Using the value of a, given above and the fact that the unpaired electron is in theT-system, calculate the spin density on the nearest neighbor carbon.6. The 1'C hyperfine coupling in the methyl radical is 41 gauss, and the proton hyperfinecoupling is 23 gauss. Sketch the spectrum expected for 13.CH, radical. [For answer,scc T. Cole et al., Mol. Phys., 1, 406 (1958).]7. Assume that all hyperfine lines can be resolved and sketch the spectrum for thechlorobenzene anion radical.8. Assuming all other factors constant, would line broadening be greater for a bimolecularprocess with a rate constant of 107 or with a rate constant of 1010?9. How many lines would you expect in the epr spectrum of (CN),CoO,Co(NH,),?Explain.10. The spectrum below is obtained for the NH,radical:a. Convert it to an absorption spectrum.b. How could you determine whether the larger or smaller splitting is due to hydrogen?c. Assume that the larger splitting is due to nitrogen. Construct a diagram similar toFig. 9–10 to explain the spectrum.

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