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Mass spectra of metal iodides
Tahta,
Vol. 22, pp. 695497.
Pergamon
Press, 1975. Pnated in Great Britain
ANALYTICAL
MASS SPECTRA Kozo
DATA
OF METAL
IODIDES
MATSUMOTO,NOBUTCSHIKIBA and TSJGIOTAKEUCHI
Department of Synthetic Chemistry, Nagoya University, Nagoya, Japan (Received 24 October 1974. Accepted 14 January 1975)
In our laboratory, the quantitative determination of metal halides has been studied by mass spectrometry as a method of determination of trace amounts of metals. In previous papers mass spectra of several metal chlorides were reported, 1*2.3 but the mass spectra of alkali metal chlorides could not be obtained, because of their low volatility. As the vapour pressure of metal iodides is generally higher than that of the chlorides, attempts were ma& to measure the mass spectra of alkali metal iodides. It was found possible to record the mass spectra of LiI, NaI, KI, RbI, and CsI as well as those of AsIs, SbIs, Sr&, CuI, and Pb12. EXPERIMENTAL
All reagents used were of super pure grade. The instrument used in this study was a JMS-OlSG double focusing mass spectrometer, JALCO. The operational conditions were as follows: main slit 20 or 8 pm; acceleration voltage 7 kV; ionization voltage 75 or 20 V; ionization current 200 4; sample temperatures loo-400”.
166 (KI+), 205 (K,I+) and 254 (12+) were observed, and other peaks at m/e 23 Na+ (calculated mass; 22990, observed mass; 22.987), 150 (NaI+), 189 NaKI+ (calculated mass; 188.858, observed mass; 188.858) and 133 (Cs’) also appeared. Table 4 summarizes the mass spectrum of rubidium iodide. In this spectrum peaks at m/e 85 (Rb+), 127 (I+), 128 (HI+), 212 (RbI+), 254 (Is+), 297 (Rb,I+) and 339 (RbI:) were observed. Other peaks from contamination also appeared at m/e 23 (Na+), 150 (NaI+), 166 (KI+k 133 (Cs+) and 260 (CsI+). Table 5 summarizes the mass spectrum of caesium iodide. In this spectrum peaks at m/e 635 (I”), 127 (I+), 133 (Cs’), 254 (Ir+), 260 (CsI+) and 393 (C@) were observed and no other peak appeared. From these results, it appeared possible to detect various .alkali metals by mass spectrometry. Table 2. Mass spectrum of sodium iodide (sample temperature 35O’C)
RESULTS
Table 1 summarizes the mass spectrum of lithium iodide. In this mass spectrum peaks at m/e 7 (Li+), 127 (I’), 134 (LiI+), 141 (LizI+), and 254 (12+) and additional peaks at m/e 23 (Na+, calculated mass; 22990, observed mass; 22*987), 150 (NaI+, calculated mass; 149.894, observed mass; 149.895) and 157 (LiNaI*, calculated mass; 156.910, observed mass; 156906) appeared. The additional peaks were also observed in the mass spectra of other commercial samples of lithium iodide, which suggests that some sodium iodide is contained even in the super pure grade lithium iodide. Table 2 summarizes the mass spectrum of sodium iodide. In addition to the characteristic peaks of sodium iodide, a peak at m/e 166 was assigned to KI+ (calculated mass; 165.868, observed mass; 165*867),which originated from contamination of the sodium iodide. Table 3 summarizes the mass spectrum of potassium iodide. In this spectrum peaks at m/e 39 (K+), 127 (I+),
m/e 23 63.5 127 128 150 166 173 254
7 23 63.5 127 128 134 140 141 157 254
Ion Li+ Na+ 12+ 1+ HI+ LiI+ 6Li7LiI+ ‘L&I+ NaLiI+ I2+
Relative intensity, y0
Na? 12+ I+ HI+ NaI+ KI+ Na,J’ I2 +
56.4 53.3 39.0 8.2 954 35.4 100 44.6
Table 3. Mass spectrum of potassium iodide (sample temperature 420°C)
Table 1. Mass spectrum of lithium iodide (sample temperature 380°C)
m/e
Ion
Relative intensity, % 9.3 2.2 7.3 179 5.1 4.6 100 7.9 3.9 405 695
mle 23 39 41 63.5 85 87 127 128 133 150 166 168 189 205 207 254
Ion Na+ 39K+ .+iK+ Is+ ‘=Rb+ s’Rb+ I+ HI+ cs+ NaI+ asKI+ *‘KI+ NaIK+ s9K21+ agKd’KI+ I2 +
Relative intensity, y0 74.6 47,6 3.4 100 11.1 4.1 79.4 44.4 71.4 952 36.6 3.2 38.1 47.6 9.5 7,9
696
ANALYTICAL
Table 4. Mass spectrum of rubidium iodide (sample temperature 380°C)
mle
Ion
23 85 87 127 128 133 150 166 212 214 254 260 297 299 30 339 341
Na+ =-Rb+ s’Rb+ 1+ HI+ cs+ NaI+ KI+ s’RbI+ 87RbI+ 2: s5RbzI+ sSRb*‘RbI+ *‘RbrI+ =RbIz+ s’RbIr +
Relative intensity, % 5.1 96.6 37.2 97.4 5.1 100 7.7 11.5 41.0 15.4 7.7 23.1 6.4 51 1.2 3.8 1.5
DATA
Table 7. Mass spectrum of antimony tri-iodide (sample temperature 120°C)
m/e 63.5 121 123 127 248 250 254 375 377 502 504
m/e 63.5 127 133 254 260 393
Ion
Relative intensity, %
I*+ I+ cs+ 1+ c&+ cs,1+
88.3 83.3 33.3 28.3 100 11.7
Table 6. Mass spectrum of arsenic tri-iodide (sample temperature 127°C)
m/e 63.5 127 202 254 329 456
Ion
Relative intensity, %
12+ I+ AsI+ I2 + AsI, + AsI, +
8 100 24 55 44 72
Mass spectra of AsIs, Sbl,, Snl,
Cul and Pblz
Table 6 summarizes the mass spectrum of arsenic triiodide. Arsenic is a monoisotopic element, and provides a simple spectrum. Table 7 summarizes the mass spectrum of antimony tri-iodide. Antimony has two natural stable isotopes ( iZISb and iz3Sb) and this spectrum was more complex. Table 8 summarizes the mass spectrum of tin tetraiodide. Since tin has ten natural stable isotopes, the mass spectrum is even more complex. Table 9 summarizes the mass spectrum of copper(I) iodide. Copper has two natural stable isotopes (L3Cu and %Zu). In this spectrum peaks at m/e values higher than that of CuI+ were observed. These peaks are due to the ions Cu31:, Cu31:,
Iz+ tZlSb+ 123Sb+ I+ 12’SbI+ 123SbI+ IZC iz1Sb12+ 123Sb12+ i21Sb13+ ‘?Sb13 +
Relative intensity, % 4.4 28.6 22.0 100 24.2 18.9 6.6 42.9 31.9 36.3 26.4
Table 8. Mass spectrum of tin tetraiodide perature 220°C)
mle
Table 5. Mass spectrum of caesium iodide (sample temperature 400°C)
Ion
116 118 120 127 243 245 247 254 371 373 375 497 499 501 624 626 628
Ion 1 lesn+
iisfjnt 120cJn+
I+ ii%nI+ “sSnI+ 120SnI+ It ’ ‘%I, + “sSn12 + lzoSn12+ “%n13 + “%I3 + i20Sn13+ “%nI,+ 118Sn14+ 120Snla+
(sample tem-
Relative intensity, % 5.3 9.9 12.5 100 8.8 13.8 18.8 100 2.5 3.8 6.3 &8 125 17.5 7.5 100 13.8
Table 9. Mass spectrum of copper (I) iodide (sample temperature 280°C)
m/e 63 63.5 65 126 127 128 130 190 192 253 254 255 257 380 382 384 443 445 447 449 570 572 574 576
Ion
Relative intensity, %
WU+ 12+ Wu+ %Li: I+ 63cu65cu+ 6Qlz + 6”CUIf %ll1+ Yl121+ IZ+ 63cu65cuI+ Wu21+ 6’cu212+ Wll~5cuI+ Wu21* + 6’cu31z+ Wu,WuI, + Wu~5cu212+ 65cu312+ 63Cu313+ ~3cu2~5cu13+ 63cuWu213 + Wu313 +
41 10 18 26 52 15 7 100 48 76 47 65 12 9 7 2 44 57 25 3 66 85 38 5
ANALYTICAL
Table 10. Mass spectrum of lead(H) iodide (sample temperature 260°C)
m/e 63.5 127 128 206 207 208 331 333 334 335 458 460 461 462
Ion Is+ I+ HI+ zoSPb+ solPb+ 208pbf
‘04PbI+ ‘06PbI+ “‘PbI+ *08PbI+ 204Pb12+ so6PbI, + 207Pb12+ zosPb12+
Relative intensity, y0 8.6 100 8.6 4 4 10 2 27 23 52 1 17 15 36
697
DATA
Cu&, and CuJ+. A -peak due to the Cur+ ion also appeared. Table 10 summarizes the mass spectrum of lead(II) iodide. Lead has four natural stable isotopes, but this spectrum was very simple. The: mass spectra of metal iodides were in general simpler than those of the metal chlorides reported earlier, because of the monoisotopic nature of iodine. Acknowledgment-The authors are deeply grateful to Dr. S. Tsuge of this department for useful discussions.
REFRRENCES
1. K. Matsumoto, N. Kiba, and T. Takeuchi, Anal. Chem., 1971, 43, 1691. 2. K. Matsumoto, Y. Sasaki, and T. Takeuchi, ibid., 1972, 44, 2264. 3. K. Matsumoto, N. Kiba, and T. Takeuchi, Talanta, 1975, 22. 321.
Summary-The mass spectra of LiI, NaI, KI, RbI, CsI, AsIs, SbIs, SnI,, CuI and PbIr have been recorded. and trace contaminants in alkali metal iodides detected.
Vol. 22, pp. 695497.
Pergamon
Press, 1975. Pnated in Great Britain
ANALYTICAL
MASS SPECTRA Kozo
DATA
OF METAL
IODIDES
MATSUMOTO,NOBUTCSHIKIBA and TSJGIOTAKEUCHI
Department of Synthetic Chemistry, Nagoya University, Nagoya, Japan (Received 24 October 1974. Accepted 14 January 1975)
In our laboratory, the quantitative determination of metal halides has been studied by mass spectrometry as a method of determination of trace amounts of metals. In previous papers mass spectra of several metal chlorides were reported, 1*2.3 but the mass spectra of alkali metal chlorides could not be obtained, because of their low volatility. As the vapour pressure of metal iodides is generally higher than that of the chlorides, attempts were ma& to measure the mass spectra of alkali metal iodides. It was found possible to record the mass spectra of LiI, NaI, KI, RbI, and CsI as well as those of AsIs, SbIs, Sr&, CuI, and Pb12. EXPERIMENTAL
All reagents used were of super pure grade. The instrument used in this study was a JMS-OlSG double focusing mass spectrometer, JALCO. The operational conditions were as follows: main slit 20 or 8 pm; acceleration voltage 7 kV; ionization voltage 75 or 20 V; ionization current 200 4; sample temperatures loo-400”.
166 (KI+), 205 (K,I+) and 254 (12+) were observed, and other peaks at m/e 23 Na+ (calculated mass; 22990, observed mass; 22.987), 150 (NaI+), 189 NaKI+ (calculated mass; 188.858, observed mass; 188.858) and 133 (Cs’) also appeared. Table 4 summarizes the mass spectrum of rubidium iodide. In this spectrum peaks at m/e 85 (Rb+), 127 (I+), 128 (HI+), 212 (RbI+), 254 (Is+), 297 (Rb,I+) and 339 (RbI:) were observed. Other peaks from contamination also appeared at m/e 23 (Na+), 150 (NaI+), 166 (KI+k 133 (Cs+) and 260 (CsI+). Table 5 summarizes the mass spectrum of caesium iodide. In this spectrum peaks at m/e 635 (I”), 127 (I+), 133 (Cs’), 254 (Ir+), 260 (CsI+) and 393 (C@) were observed and no other peak appeared. From these results, it appeared possible to detect various .alkali metals by mass spectrometry. Table 2. Mass spectrum of sodium iodide (sample temperature 35O’C)
RESULTS
Table 1 summarizes the mass spectrum of lithium iodide. In this mass spectrum peaks at m/e 7 (Li+), 127 (I’), 134 (LiI+), 141 (LizI+), and 254 (12+) and additional peaks at m/e 23 (Na+, calculated mass; 22990, observed mass; 22*987), 150 (NaI+, calculated mass; 149.894, observed mass; 149.895) and 157 (LiNaI*, calculated mass; 156.910, observed mass; 156906) appeared. The additional peaks were also observed in the mass spectra of other commercial samples of lithium iodide, which suggests that some sodium iodide is contained even in the super pure grade lithium iodide. Table 2 summarizes the mass spectrum of sodium iodide. In addition to the characteristic peaks of sodium iodide, a peak at m/e 166 was assigned to KI+ (calculated mass; 165.868, observed mass; 165*867),which originated from contamination of the sodium iodide. Table 3 summarizes the mass spectrum of potassium iodide. In this spectrum peaks at m/e 39 (K+), 127 (I+),
m/e 23 63.5 127 128 150 166 173 254
7 23 63.5 127 128 134 140 141 157 254
Ion Li+ Na+ 12+ 1+ HI+ LiI+ 6Li7LiI+ ‘L&I+ NaLiI+ I2+
Relative intensity, y0
Na? 12+ I+ HI+ NaI+ KI+ Na,J’ I2 +
56.4 53.3 39.0 8.2 954 35.4 100 44.6
Table 3. Mass spectrum of potassium iodide (sample temperature 420°C)
Table 1. Mass spectrum of lithium iodide (sample temperature 380°C)
m/e
Ion
Relative intensity, % 9.3 2.2 7.3 179 5.1 4.6 100 7.9 3.9 405 695
mle 23 39 41 63.5 85 87 127 128 133 150 166 168 189 205 207 254
Ion Na+ 39K+ .+iK+ Is+ ‘=Rb+ s’Rb+ I+ HI+ cs+ NaI+ asKI+ *‘KI+ NaIK+ s9K21+ agKd’KI+ I2 +
Relative intensity, y0 74.6 47,6 3.4 100 11.1 4.1 79.4 44.4 71.4 952 36.6 3.2 38.1 47.6 9.5 7,9
696
ANALYTICAL
Table 4. Mass spectrum of rubidium iodide (sample temperature 380°C)
mle
Ion
23 85 87 127 128 133 150 166 212 214 254 260 297 299 30 339 341
Na+ =-Rb+ s’Rb+ 1+ HI+ cs+ NaI+ KI+ s’RbI+ 87RbI+ 2: s5RbzI+ sSRb*‘RbI+ *‘RbrI+ =RbIz+ s’RbIr +
Relative intensity, % 5.1 96.6 37.2 97.4 5.1 100 7.7 11.5 41.0 15.4 7.7 23.1 6.4 51 1.2 3.8 1.5
DATA
Table 7. Mass spectrum of antimony tri-iodide (sample temperature 120°C)
m/e 63.5 121 123 127 248 250 254 375 377 502 504
m/e 63.5 127 133 254 260 393
Ion
Relative intensity, %
I*+ I+ cs+ 1+ c&+ cs,1+
88.3 83.3 33.3 28.3 100 11.7
Table 6. Mass spectrum of arsenic tri-iodide (sample temperature 127°C)
m/e 63.5 127 202 254 329 456
Ion
Relative intensity, %
12+ I+ AsI+ I2 + AsI, + AsI, +
8 100 24 55 44 72
Mass spectra of AsIs, Sbl,, Snl,
Cul and Pblz
Table 6 summarizes the mass spectrum of arsenic triiodide. Arsenic is a monoisotopic element, and provides a simple spectrum. Table 7 summarizes the mass spectrum of antimony tri-iodide. Antimony has two natural stable isotopes ( iZISb and iz3Sb) and this spectrum was more complex. Table 8 summarizes the mass spectrum of tin tetraiodide. Since tin has ten natural stable isotopes, the mass spectrum is even more complex. Table 9 summarizes the mass spectrum of copper(I) iodide. Copper has two natural stable isotopes (L3Cu and %Zu). In this spectrum peaks at m/e values higher than that of CuI+ were observed. These peaks are due to the ions Cu31:, Cu31:,
Iz+ tZlSb+ 123Sb+ I+ 12’SbI+ 123SbI+ IZC iz1Sb12+ 123Sb12+ i21Sb13+ ‘?Sb13 +
Relative intensity, % 4.4 28.6 22.0 100 24.2 18.9 6.6 42.9 31.9 36.3 26.4
Table 8. Mass spectrum of tin tetraiodide perature 220°C)
mle
Table 5. Mass spectrum of caesium iodide (sample temperature 400°C)
Ion
116 118 120 127 243 245 247 254 371 373 375 497 499 501 624 626 628
Ion 1 lesn+
iisfjnt 120cJn+
I+ ii%nI+ “sSnI+ 120SnI+ It ’ ‘%I, + “sSn12 + lzoSn12+ “%n13 + “%I3 + i20Sn13+ “%nI,+ 118Sn14+ 120Snla+
(sample tem-
Relative intensity, % 5.3 9.9 12.5 100 8.8 13.8 18.8 100 2.5 3.8 6.3 &8 125 17.5 7.5 100 13.8
Table 9. Mass spectrum of copper (I) iodide (sample temperature 280°C)
m/e 63 63.5 65 126 127 128 130 190 192 253 254 255 257 380 382 384 443 445 447 449 570 572 574 576
Ion
Relative intensity, %
WU+ 12+ Wu+ %Li: I+ 63cu65cu+ 6Qlz + 6”CUIf %ll1+ Yl121+ IZ+ 63cu65cuI+ Wu21+ 6’cu212+ Wll~5cuI+ Wu21* + 6’cu31z+ Wu,WuI, + Wu~5cu212+ 65cu312+ 63Cu313+ ~3cu2~5cu13+ 63cuWu213 + Wu313 +
41 10 18 26 52 15 7 100 48 76 47 65 12 9 7 2 44 57 25 3 66 85 38 5
ANALYTICAL
Table 10. Mass spectrum of lead(H) iodide (sample temperature 260°C)
m/e 63.5 127 128 206 207 208 331 333 334 335 458 460 461 462
Ion Is+ I+ HI+ zoSPb+ solPb+ 208pbf
‘04PbI+ ‘06PbI+ “‘PbI+ *08PbI+ 204Pb12+ so6PbI, + 207Pb12+ zosPb12+
Relative intensity, y0 8.6 100 8.6 4 4 10 2 27 23 52 1 17 15 36
697
DATA
Cu&, and CuJ+. A -peak due to the Cur+ ion also appeared. Table 10 summarizes the mass spectrum of lead(II) iodide. Lead has four natural stable isotopes, but this spectrum was very simple. The: mass spectra of metal iodides were in general simpler than those of the metal chlorides reported earlier, because of the monoisotopic nature of iodine. Acknowledgment-The authors are deeply grateful to Dr. S. Tsuge of this department for useful discussions.
REFRRENCES
1. K. Matsumoto, N. Kiba, and T. Takeuchi, Anal. Chem., 1971, 43, 1691. 2. K. Matsumoto, Y. Sasaki, and T. Takeuchi, ibid., 1972, 44, 2264. 3. K. Matsumoto, N. Kiba, and T. Takeuchi, Talanta, 1975, 22. 321.
Summary-The mass spectra of LiI, NaI, KI, RbI, CsI, AsIs, SbIs, SnI,, CuI and PbIr have been recorded. and trace contaminants in alkali metal iodides detected.