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Atkins, Solution, 7th Ed

Atkins, Solution, 7th Ed

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Atkins, 7th edition solutions manual
Atkins, 7th edition solutions manual

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03/18/2014

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18 Spectroscopy 3: magnetic resonance
Solutions to exercises
Discussion questions
E18.1(b)Before the application of a pulse the magnetization vector,M, points along the direction of the static

external magnetic \ufb01eldB0. There are more\u03b1 spins than\u03b2 spins. When we apply a rotating magnetic \ufb01eldB1 at right angles to the static \ufb01eld, the magnetization vector as seen in the rotating frame begins to precess about theB1\ufb01eld with angular frequency\u03c91=\u03b3B1. The angle through whichM rotates is

\u03b8= \u03b3B1t, where tis the time for which theB1pulse is applied. When t= \u03c0/2\u03b3B1, \u03b8= \u03c0/2= 90\u25e6,
andM has rotated into the xy plane. Now there are equal numbers of\u03b1 and\u03b2 spins. A 180\u25e6pulse
applied for a time\u03c0/\u03b3B1, rotatesM antiparallel to the static \ufb01eld. Now there are more\u03b2 spins than
\u03b1spins. A population inversion has occurred.
E18.2(b)The basic COSY experiment uses the simplest of all two-dimensional pulse sequences: a single
90\u25e6pulse to excite the spins at the end of the preparation period, and a mixing period containing just
a second 90\u25e6 pulse (see Fig. 18.44 of the text).

The key to the COSY technique is the effect of the second 90\u25e6pulse, which can be illustrated by consideration of the four energy levels of an AX system (as shown in Fig. 18.12). At thermal equilibrium, the population of the\u03b1A\u03b1X level is the greatest, and that of\u03b2 A\u03b2 X level is the smallest; the other two levels have the same energy and an intermediate population. After the \ufb01rst 90\u25e6 pulse, the spins are no longer at thermal equilibrium. If a second 90\u25e6pulse is applied at a time t1 that is short compared to the spin-lattice relaxation time T1the extra input of energy causes further changes in the populations of the four states. The changes in populations will depend on how far the individual magnetizations have precessed during the evolution period.

For simplicity, let us consider a COSY experiment in which the second 90\u25e6pulse is split into two selective pulses, one applied to X and one to A. Depending on the evolution timet1, the 90\u25e6 pulse that excites X may leave the population differences across each of the two X transitions unchanged, inverted, or somewhere in between. Consider the extreme case in which one population difference is inverted and the other unchanged (Fig. 18.45). The 90\u25e6pulse that excites A will now generate an FID in which one of the two A transitions has increased in intensity, and the other has decreased. The overall effect is that precession of the X spins during the evolution period determines the amplitudes of the signals from the A spins obtained during the detection period. As the evolution time t1 is increased, the intensities of the signals from A spins oscillate at rates determined by the frequencies of the two X transitions.

This transfer of information between spins is at the heart of two-dimensional NMR spectroscopy and leads to the correlation of different signals in a spectrum. In this case, information transfer tells us that there is a scalar coupling between A and X. If we conduct a series of experiments in which t1is incremented, Fourier transformation of the FIDs on t2yields a set of spectraI (\u03bd1,\u03bd2)in which the A signal amplitudes oscillate as a function of t1. A second Fourier transformation, this time on t1, converts these oscillations into a two-dimensional spectrumI (\u03bd1, \u03bd2 ). The signals are spread out in\u03bd1according to their precession frequencies during the detection period. Thus, if we apply the COSY pulse sequence to our AX spin system (Fig. 18.44), the result is a two-dimensional spectrum that contains four groups of signals centred on the two chemical shifts in\u03bd1and\u03bd2. Each group will show \ufb01ne structure, consisting of a block of four signals separated byJAX. The diagonal peaks are signals centerd on(\u03b4A\u03b4A)and (\u03b4X\u03b4X)and lie along the diagonal \u03bd1=\u03bd2. They arise from signals that did not change chemical shift betweent1 andt2. The cross peaks (oroff-diagonal peaks) are signals centred on(\u03b4A\u03b4X)and (\u03b4X\u03b4A)and owe their existence to the coupling between A and X.

SPECTROSCOPY 3: MAGNETIC RESONANCE
291

Consequently, cross peaks in COSY spectra allow us to map the couplings between spins and to trace out the bonding network in complex molecules. Figure 18.46 shows a simple example of a proton COSY spectrum of 1-nitropropane.

E18.3(b)The molecular orbital occupied by the unpaired electron in an organic radical can be identi\ufb01ed

through the observation of hyper\ufb01ne splitting in the EPR spectrum of the radical. The magnitude of this splitting is proportional to the spin density of the unpaired electron at those positions in the radical having atoms with nuclear moments. In addition, the spin density on carbon atoms adjacent to the magnetic nuclei can be determined indirectly through the McConnell relation. Thus, for example, in the benzene negative ion, unpaired spin densities on both the carbon atoms and hydrogen atoms can be determined from the EPR hyper\ufb01ne splittings. The next step then is to construct a molecular orbital which will theoretically reproduce these experimentally determined spin densities. A good match indicates that we have found a good molecular orbital for the radical.

Numerical exercises
E18.4(b)For19F\u00b5
\u00b5N
=2.62835, g =5.2567
\u03bd= \u03bdL=\u03b3B
2\u03c0with\u03b3=gI \u00b5N
\u00af
h
Hence,\u03bd=gI \u00b5NB
h
=(5.2567)\u00d7 (5.0508\u00d7 10\u221227JT\u22121)\u00d7 (16.2T)
(6.626\u00d7 10\u221234 J s)
=6.49 \u00d7108s\u22121=649 MHz
E18.5(b)
EmI=\u2212\u03b3\u00af
hBmI=\u2212gI \u00b5NBmI
mI=1,0,\u22121
EmI= \u2212(0.404) \u00d7(5.0508 \u00d710\u221227 J T\u22121) \u00d7(11.50 T)mI
= \u2212(2.3466 \u00d710\u221226 J)mI
\u22122.35 \u00d710\u221226 J, 0, +2.35 \u00d710\u221226 J
E18.6(b)The energy separation between the two levels is
\ue000E= h\u03bdwhere \u03bd=\u03b3B
2\u03c0=(1.93\u00d7 107T\u22121s\u22121)\u00d7 (15.4T)
2\u03c0
=4.73 \u00d7107 s\u22121 =47.3 MHz
E18.7(b)A 600 MHz NMR spectrometer means 600 MHz is the resonance \ufb01eld for protons for which the
magnetic \ufb01eld is 14.1 T as shown in Exercise 18.4(a). In high-\ufb01eld NMR it is the \ufb01eld not the
frequency that is \ufb01xed.
(a)A14N nucleus has three energy states in a magnetic \ufb01eld corresponding tomI= +1, 0,\u22121.
But\ue000E(+1\u2192 0)= \ue000E(0\u2192\u22121)
\ue000E= Em\ue000I\u2212 EmI=\u2212\u03b3\u00af
hBm\ue000I\u2212 (\u2212\u03b3\u00af
hBmI )
= \u2212\u03b3\u00af
hB(m\ue000I\u2212 mI )=\u2212\u03b3\u00af
hB\ue000mI
The allowed transitions correspond to\ue000mI=\u00b11; hence
\ue000E= h\u03bd= \u03b3\u00af
hB= gI\u00b5NB=(0.4036) \u00d7(5.051 \u00d710\u221227 J T\u22121) \u00d7(14.1T)
=2.88\u00d7 10\u221226 J
292
INSTRUCTOR\u2019S MANUAL
(b)We assume that the electrong-value in the radical is equal to the free electrong-value,ge=
2.0023. Then
\ue000E= h\u03bd= ge\u00b5BB[37]= (2.0023)\u00d7 (9.274\u00d7 10\u221224 J T\u22121)\u00d7 (0.300 T)
=5.57 \u00d710\u221224J
Comment. The energy level separation for the electron in a free radical in an ESR spectrometer is
far greater than that of nuclei in an NMR spectrometer, despite the fact that NMR spectrometers
normally operate at much higher magnetic \ufb01elds.
E18.8(b)
\ue000E= h\u03bd= \u03b3\u00af
hB= gI \u00b5NB[Exercise 18.4(a)]
Hence,B=h\u03bd
gI \u00b5N
=(6.626\u00d7 10\u221234J Hz\u22121)\u00d7 (150.0\u00d7 106Hz)
(5.586)\u00d7 (5.051\u00d7 10\u221227 J T\u22121)
=3.523 T
E18.9(b)In all cases the selection rule\ue000mI=\u00b11 is applied; hence (Exercise 18.7(b)(a))
B=h\u03bd
gI \u00b5N
=6.626\u00d7 10\u221234J Hz\u22121
5.0508\u00d7 10\u221227 J T\u22121\u00d7\u03bd
gI
=(1.3119 \u00d710\u22127) \u00d7
\ue000
\u03bd
Hz
\ue001
gI
T=(0.13119)\u00d7
\ue000
\u03bd
MHz
\ue001
gI
T
We can draw up the following table
B/T
14N
19F
31P
gI
0.40356 5.2567 2.2634
(a)300 MHz
97.5
7.49
17.4
(b)750 MHz
244
18.7
43.5
Comment. Magnetic \ufb01elds above 20 T have not yet been obtained for use in NMR spectrometers.

As discussed in the solution to Exercise 18.7(b), it is the \ufb01eld, not the frequency, that is \ufb01xed in high-\ufb01eld NMR spectrometers. Thus an NMR spectrometer that is called a 300 MHz spectrometer refers to the resonance frequency for protons and has a magnetic \ufb01eld \ufb01xed at 7.05 T.

E18.10(b)The relative population difference for spin\u22121
2nuclei is given by
\u03b4N
N=N\u03b1\u2212 N\u03b2
N\u03b1+ N\u03b2
\u2248\u03b3\u00af
hB
2kT=gI\u00b5NB
2kT
[Justi\ufb01cation 18.1]
=
1.405(5.05\u00d7 10\u221227 J T\u22121)B
2(1.381\u00d7 10\u221223 J K\u22121)\u00d7 (298 K)=8.62 \u00d710\u22127(B/T)
(a)For 0.50 T\u03b4N
N=(8.62 \u00d710\u22127) \u00d7(0.50) =4.3 \u00d710\u22127
(b)For 2.5 T\u03b4N
N=(8.62 \u00d710\u22127) \u00d7(2.5) =2.2 \u00d710\u22126
(c)For 15.5 T\u03b4N
N=(8.62 \u00d710\u22127) \u00d7(15.5) =1.34 \u00d710\u22125

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