Skoog/Holler/Crouch Chapter 20

Principles of Instrumental Analysis, 7th ed.

CHAPTER 20
20-1. With gaseous ionization sources, the sample is first volatilized (by heating if necessary)

and then transmitted to the ionization area for ionization. In a desorption source, a probe

is used and ionization takes place directly from the condensed phase. The advantage of

desorption ionization is that it can be applied to high molecular weight and thermally

unstable samples. The advantage of gaseous ionization sources are their simplicity and

speed (no need to use probe and wait for probed area to be pumped out).

20-2. The most fragmentation and thus the most complex spectra are encountered with electron

ionization. Field ionization produces the simplest spectra. Chemical and electron

ionization result in higher sensitivities than does field ionization.

20-3. Both field ionization and field desorption ionization are performed at anodes containing

numerous sharp tips so that very high electrical fields are realized. In field ionization, the

sample is volatilized before ionization, whereas field desorption takes place at an anode

that has been coated with the sample. The latter requires the use of a sample probe.

20-4. (a) The total kinetic energy acquired by an electron moving between the filament and the

target will be eV, where e is the charge on the electron and V is the potential difference.

Because SS is approximately half way between the filament and the target, the total

difference in potential must be 140 V, if the electron is to have 70 eV of energy at SS.

(b) An ion formed at point P will almost certainly collide with a solid part of the exit slit

as a result of the repeller-accelerating plate voltage.

1
©2018 Cengage Learning. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
Principles of Instrumental Analysis, 7th ed. Chapter 20

20-5. (a) For CH +4 , m/z = 16 and

B 2 r 2e
16 = = kB 2 = k × (0.126 T) 2 (Equation 20-9)
2V

Similarly for m/z = 300

300 = kB2

Dividing the second equation by the first yields

300 B2
=
16 (0.126 T)2

B = 0.546 T

Thus, to scan the range of m/z from 16 to 300, the field strength would be scanned from

0.126 to 0.546 T.

(b) Here, Equation 20-9 takes the form

B 2 r 2e k ′ k′
16 = = =
2V V 3.00 × 103

At m/z = 300

300 = k′/V

Dividing the first equation by the second gives

16 k ′ / 3.00 × 103 V
= =
300 k′ / V 3.00 × 103

or

V = 16 × 3.00 × 103/300 = 160 V

Thus, scan from 3000 to 160 V.

2
©2018 Cengage Learning. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
Principles of Instrumental Analysis, 7th ed. Chapter 20

20-6. Here,

g 1 mol 1 kg kg
m = 5000 × × 3 = 8.306 × 10−24
mol 6.02 × 10 ions
23
10 g ion

Substituting into Equation 20-9 gives, after rearranging,

(0.240 Vs/m2 )2 (0.127 m) 2 × 1.60 × 10−19 C/ion (Vs)2 C

V = = 8.95 = 8.95 V
2 × 8.306 × 10−24 kg/ion m 2kg

20-7. After acceleration the velocity v can be calculated with the aid of Equation 20-4. Thus,

zeV = ½ mv2

where m for cyclohexane (M = 84) is given by

+
g C6 H12 1 mol 1 kg kg
m = 84.0 × × 3 = 1.395 × 10−25
mol 6.02 × 10 ions
23
10 g ion

2zeV 2 × 1.60 × 10−19 C/ion × 10.00 (Vs)2C/(m2 kg)

v= = −25
= 4.79 × 103 m/s
m 1.395 ×10 kg/ion

15.0 cm × 10−2 m/cm

time = = 3.13 × 10−5 s = 31.3 µs
4.79 × 10 m/s
3

20-8. The presence of a negative dc voltage in the yz plane causes positive ions to move toward

the rods where they are annihilated. In the presence of an added ac voltage, this

movement is inhibited during the positive half of the cycle with the lighter ions being

more affected than the heavier ions. Thus the yz plane acts as a low-pass filter removing

heavier ions (see Figure 11-8).

20-9. The resolution of a single focusing mass spectrometer is limited by the initial kinetic

energy spread of the sample molecules. This spread is minimized in a double focusing

instrument by accelerating the sample through an electrostatic analyzer, which limits the

3
©2018 Cengage Learning. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
Principles of Instrumental Analysis, 7th ed. Chapter 20

range of kinetic energies of ions being introduced into the magnetic sector analyzer.

Significantly narrower peaks are the result.

20-10. A quadrupole ion trap is similar to a linear quadrupole filter except it as a spherical 3-

dimensional configuration. By a combination of fields, ions are temporarily stored within

the trap. They are then released sequentially by increasing the radio frequency voltage

applied to the ring electrode. The ejected ions then strike a detector. A plot of detector

signal vs. the radio frequency voltage, related to the m/z value, is the mass spectrum. In

an FT ICR instrument, ions are trapped in a cell by an electric trapping voltage and a

magnetic field. Each ion assumes a circular motion in a plane perpendicular to the

direction of the field. The cyclotron frequency depends on the inverse of the m/z value.

In modern instruments a radio frequency pulse that increases linearly in frequency is

employed. A time domain image current is generated after termination of the pulse.

Fourier transformation of the time decay signal yields the mass spectrum.

20-11. Resolution = m/Δm

(a) m = (28.0187 +28.0061)/2 = 28.012

m/Δm = 28.012/(28.0187 – 28.0061 = 2.22 × 103

(b) m/Δm = 28.013/(28.0313 – 27.9949) = 770

(c) m/Δm = 85.0647/(85.0653 – 85.0641) = 7.09 × 104

(d) m/Δm = 286.158/(286.1930 – 286.1240) = 4.15 × 103

4
©2018 Cengage Learning. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
Principles of Instrumental Analysis, 7th ed. Chapter 20

20-12.

20-13. (a) In Table 20-3, we find that for every 100 79Br atoms there are 98 81Br atoms.

Because the compound in question has two atoms of bromine

(M + 2)+/M+ = 2 × 98/100 = 1.96

and

(M + 4)+/M+ = (98/100)2 = 0.96

(b) Table 20-3 reveals that for every 100 35Cl atoms there are 32.5 37Cl atoms. Thus,

(M + 2)+/M+ = (1 × 98/100) + (1 × 32.5/100) = 1.30

(M + 4)+/M+ = (1 × 98/100) × (1 × 32.5/100) = 0.32

(c) (M + 2)+/M+ = 2 × 32.5/100 = 0.65

(M + 4)+/M+ = (0.325/100)2 = 0.106

20-14. (a) Because all conditions except accelerating voltage are constant, Equation 20-9 can be

abbreviated to (m/z)s = K/Vs and (m/z)u = K/Vu

5
©2018 Cengage Learning. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
Principles of Instrumental Analysis, 7th ed. Chapter 20

where the subscripts s and u designate standard and unknown respectively. Dividing one

of these equations by the other gives the desired relationship.

( m / z )s K / Vs Vu
= =
(m / z ) u K / Vu Vs

69.00
(b) = 0.965035
(m / z ) u

(m/z)u = 71.50

(c) The approximately half-integral m/z value suggests that the ion being studied in part

(b) was doubly charged. This conclusion is in agreement with the fact that the molecular

mass of the unknown is 143. The second conclusion is that the unknown must contain an

odd number of nitrogen atoms.

20-15. The difference in mass between 12C and 13C is 1.00335. Therefore, making the

assumption that (P + 1)+ is due only to 13C means

mass (P + 1)+ = mass P+ + 1.00335

In Problem 20-14, we derived the following relationship

( m / z )s V
= u
(m / z ) u Vs

Taking into account the fact that only singly charged ions were specified, and rewriting

this equation with V1 representing the standard and V2 the unknown, we find

m(P + ) m(P + ) V
+
= +
= 2
m(P + 1) m(P ) + 1.00335 V1

(b) Substituting the voltage ratio into the last equation allows m(P+) to be calculated

m(P + ) V
+
= 2 = 0.987753
m(P ) + 1.00335 V1

6
©2018 Cengage Learning. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.
Principles of Instrumental Analysis, 7th ed. Chapter 20

m(P+) = 80.92

20-16. In tandem in space instruments, two independent mass analyzers are used in two different

regions in space. This is a rather straight-forward way to do tandem ms and some

conventional mass spectrometers can be converted to tandem instruments. The

advantages are that it is relatively easy to take all the different types of spectra (product

ion, precursor ion, neutral loss, multidimensional. The disadvantages are that the

efficiency can be very low and thus the sensitivity can be low. Tandem in time

instruments form the ions in a certain spatial region and then at a later time expel the

unwanted ions and leave the selected ions to be dissociated and mass analyzed in the

same spatial region. The efficiency can be fairly high and the process can be repeated

many times. It is, however, only straight forward to take product ion spectra. Both

approaches require quite expensive instrumentation.

20-17. m/z = 131 due to 35Cl3CCH2+ m/z = 133 due to 37Cl35Cl2CCH2+

m/z = 135 due to 37Cl235ClCCH2+ m/z = 117 due to 35Cl3C+

m/z = 119 due to 37Cl35Cl2C+ m/z = 121 due to 37Cl235ClC+

20-18. m/z = 84 due to 35Cl2C+ m/z = 85 due to 35Cl213CH2+

m/z = 86 due to 37Cl35Cl12CH2+ m/z = 87 due to 37Cl35Cl13CH2+

m/z = 88 due to 37Cl212CH2+

7
©2018 Cengage Learning. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a publicly accessible website, in whole or in part.