collection fluid to minimize exposure of designed solely for the purpose of (2) Bradshaw, W. G.

, Lockheed Aircraft
the freshly ground Be0 powder to detecting small changes in 0’8 abun- Corp., Rept. LMSD-2312 M a.ch 1958.
Eources of spurious oxygen. dance. However, by employing B (3) Brewer, L., A.E.C. kept. MDDC,
p. 366 (1946).
Kormal concept‘ of analytical mass suitable standard of known 0 1 8 abun- (4) Evans, E., Kubaschewski, O., “Metal-
spectrometry TI ould require calibration dance, it should be equally applicable lurgical Thermo-Chemistry,” p. 305,
runs on pure COlg and CO16. Honever, to the absolute determination of 0 1 8 Butterworth-Springer Ltd., London,
since the desired end product of the 1951.
abundance in B e 0 and other metal (5) Gregory, J. K.,Mapper, D., Analyst
data gathered for this problem was only oxides which have similar vacuum 80. 230 (1955).
the change in the COIWOIG ratio fusion reactions. (6, National -Research Corp. operating
between samples nithin a set, mass Preparation of diffusion blocks, details instruction for vacuum fudon apparatus,
discrimination and calibration in- Type 912C.
of the serial grinding, and the successful (7) Sloman, H. A., Harvey, C. A.,
equalities bet\Teen C016 and CO1* reduction of the analytical data to ob- Kubaschewski, O., J. Inst. Metals 80,
were relatively unimportant and were tain diffusion coefficients for oxygen in 391 (1952).
not con4clered. The calculation of Be0 are presented in a separate report
per cent 01*is therefore based on the (1). RECBIVED for review January 8, 1963.
approximations that sensitivities are LITERATURE CITED Accepted September 3, 1963. Presented
equal and no fractionation takes place at ASTM Committee E-14 Meeting on
(1) Austerman, S. B., Meyer, R. A., Mass Spectrometry, June 8, 1961. Work
a t the molecular leak. Swarthout, D. G., “Oxygen Diffusion in was performed under AEC Contract
This technique and apparatus were Beryllium Oxide,” NAA SR 6427. AT( 11-1)-GEN-8.

A Mass Scale Based on CH,= 14.0000 for High

Resolution Mass Spectrometry of Organic Compounds
EDWARD KENDRICK’
Analytical Research Division, Esso Research and Engineering Co., linden, N. 1.

b The problems of computing, storing, ments makes possible precise mass of compounds having masses as high as
and retrieving precise masses of the measurement to a few parts in lo5 or 1000, or even higher.
many combinations of elements likely better. This is sufficient to distinguish The table of precise masses most
to occur in the mass spectra of organic between ions having the same mass widely used at present is by Beynon
compounds are considerable. They number, but different chemical com- ( I ) , which lists, in addition, the relative
can b e significantly reduced by the position. The precise mass of an ion is abundances of isotope peaks. This
adoption of a mass scale in which the the sum of the masses of its constituent table, which is based on 0l6= 16.00000,
mass of the CH2 radical is taken as elements and the molecular formula can covers combinations of elements up to a
14.0000 mass units. The advantage usually be found from the mass deter- mass number of 250, and is limited to
of this scale is that ions differing by mination. This ability to determine the those containing no more than four
one or more CH2 groups have the same chemical composition of an ion from a oxygen atoms, four nitrogen atoms, and
mass defect. The precise masses of a measurement of its mass gives mass a total of no more than six atoms other
series of alkyl naphthalene parent spectrometry a new dimension. than carbon and hydrogen. Beynon’s
peaks, for example, are 127.9195, With the advent of the high resolution table has about 6000 entries. Beynon’s
141 -91 95, 155.91 95, etc. Because mass spectrometer have come the table has recently been extended to
of the identical mass defects, the problems of computing, storing, and mass 500 and based on the standard
similar origin of these peaks is recog- comparing large amounts of mass data. C12 = 12.0000 (6). The inclusion of
nizable without reference to tables The masses of the isotopes of most sulfur (P and S8‘ isotopes) and C13
of masses. Tables of the mass de- elements are known to very high ac- would increase the size of the table
fects for combinations of H, C12, C13, curacy, but the number of combinations enormously. Over one and a half
N, 0, 5 3 2 , and Sa4are presented. of these elements in organic chemistry million entries would be required to
is extremely large. Published tables cover the ions up to mass 600.

D OUBLE focusing mass spectrom-

eters with resolutions of one
part in 5000 or better are now coming
cover only a fraction of the combinations.
Comprehensive tables of precise
mmses are required to give the precise
A mass scale with C12Ha = 14.00000
enables the same data-i.e., up to mass
6OO-to be expressed in less than
into use as analytical instruments. masses of ions used for internal calibra- 100,000 entries. This reduction is a
Commercial instruments after the tion standards in high resolution mass consequence of the same defect’s being
original design by Mattauch and Herzog spectra and to convert the precise mass repeated a t intervals of 14 mass units-
(7-9) have been described by Voorhies measurements made on samples into Le., one (CH2) group. Restrictions
and coworkers ( f a ) and by Craig and molecular formulas. Such tables are similar to those imposed by Beynon
coworkers (6). Another instrument indispensable for high resolution mass have been used for these tables. No
based on a design by Nier and Roberts spectrometry. more than four atoms of oxygen, nitro-
(4, 10-16) has been described by Craig The mass range to be covered by gen, sulfur or carbon-13 and no more
and Errock (6). Beynon (1) has these tables has no definite limit. than two atoms of sulfur-34 are allowed
pioneered the application of high resolu- High resolution mass spectrometers are in any combination. The total number
tion mass spectrometers to organic certainly capable of working in the
chemistry. range up to 500 mass numbers, and 1 Present address, Esso Research, Ltd.,
The high resolution of these instru- special applications may call for spectra Abingdon, Berkshire, England.

2146 ANALYTICAL CHEMISTRY

 Table I. Masses of Ions on CH2 Mass Scale Compared with 0l6Scale"
Masses
Element Ion 018 scale CIZHzscah
Hydrogen (")+ 1.0081451 1,006705
(Ha)+ 2.0147406 2.011878
Carbon (ClZ) + 12.0038156 11.986590
(C'3)+ 13.0074929 12.98884
Nitrogen (N14)+ 14.0075263 13.98751
Oxygen (oiaj+ 16.0000000 15.97702
Fluorine (Fig) + 19.0044429 18.97731
Neon (?\'e20)+ 19.9987953
-. . .- . - 19.97012
Phosphorus (P3l)i- 30.9836126 30.93918
Sulfur (W)+ 31.9822388 31.93631
(P"+ 33.9786635 33.92986
Chlorine (Cl9 + 34.9799720 34.92981
(c~j+ 36.9776573 36.92463
-
Areon (Ado)+
( ~ 4j0+z
39.9750928
is,9875463
39.91776
i9.95888
Gallium ( Gaeg)+ 68.94757 68.84870
(Ga7l)+ 70.94737 70,84563
Silicon (Sl*)+ 27.9456821 27.94569
.c\
a Although ClZhas now been adopted a8 the standard mass unit, most published tables
Figure 1 . Multiplet at mass 142 are based on 0l6.

Table 11. Mercury Ions on the CH2 Mass Scale

of oxygen, nitrogen. and sulfur atoms in Hg + Hg + 2 Hg +3 Hg +4
any combination has been limited to 197.74572 98.87286 65.91484 49.43643
Six. 198.74681 99,37304 66.24869 49.68682
Carlson et al. (3) hgive described a 199.74507 99.87254 66. 58069 49.93627
200.74591 100.37296 66.91530 50.18648
method of interpreting high resolution 201,74513 100.8$256 67.24838 50,43628
mass spectra in which the mass dif- 203.74575 101,87287 6 i . 91525 50.93648
ferences between an unlrnown and a ref-
erence peak a t the same mass number
are assigned to diflerecces in molecular
formula. The CH2 mrm scale has the
advantage of being applicable over a Masses given in this paper are on the number of mass numbers by defining
wider mass range and thus is of scale CH2 = 14.0000 unless otherwise the mass scale as CH2 = 14.0000.
particular value for instruments with specified. Because with CHZ= 14.0000 the defect
which it is possible to iiiterpolate over a The Basis of the CH2 Mass Scale. of the combination (CHI), is always
range of mass numbers or to determine The basis of t h e CHZ scale is best zero-e.g., CloH20 = 140.0000 and
exact masses by deter nining the ratio appreciated by considering a multiplet CsH18 = 126.0000-the defects for
of the unknown and re,'erence masses. which could arise a t a particular mass. other combinations apply at any carbon
Figure 1 shows such a multiplet a t number. Figure 3 shows the manner in
nz/e 142. These peaks could be the which the pattern is repeated.
THE CH2 MAS: SCALE parent ions of methyl naphthalene, a Kow that the zero of the mass defect
CS diketone, a CS ketone, and decane. scale has been fixed and with it the units
Masses on the OI6 scale (atomic mass The pattern presented by the peaks will in which the defects are measured, the
units) and C12scale (U) can be converted be repeated at m/e 156 for compounds defects for ions containing say one
to the CH2 scale tiy dividing by one carbon number higher in each oxygen atom can be read off. At 140, for
1.0014361 and 1.0011178, respectively. series-Le., for dimethyl naphthalene, example, the C9HI60ions would have a
The masses of some of the elemental ions a CSdiketone, a Cloketone, and undec-
encountered in mass spectrometry are ane.
giT.en in Tables I and 11. The same pattern will appear at
intermediate or lower masses if the
/'
,'
,"/

same number of protons is stripped from

each of the molecules. Thus, a t mass
140, we may find the same pattern for
ions with the formulas Ci1Hs, C8H1202,
CsHleO, and CloH~0. The spacings
between the peaks are exactly the same
as those in the other two cases. The
mass defects for ions of these species at
different mass numbers vary as the
numbers of hydrogen atoms vary, but
the differences between the defects for
the different species remain constant.
Figure 2 is a representation of the
mass defects of ions of the types
., "' previously considered containing
-
carbon, hydrogen, and one or two atoms 36 4
I _. I . b S S DEFECT x lo'
of oxygen. This diagram covers the
Figure 2. Mass defects m / e 128 to mass numbers from 128 to 142. It can Figure 3. Repetition of defects on
m / e 142 now be made to cover an infinite CH2 mass scale

VOL 35, NO. 13, DECEMBER 1963 2147

 defect of 36.4 x mass units. At
Table 111. Comparison of the Masses of 126, the ions of formula C a u O would
Some Organic Ions on the Two Scales have the same defect. The difference
in composition between the two examples
Mass scale is (CHz), which has zero defect by
016 = C'ZHz definition.
16.0000 14.0000 As an alternative to reading a chart,
Naphthalenes 128.1036 127.9196 the defects can be found from tables.
i42.1237 i 4 i . 9196 It is convenient to consider the defect
156.1439 155.9196 as the sum of contributions from the
170.1640 169.9196 hydrocarbon ion and from the separa-
etc. etc. tion of the peak from the hydrocarbon
peak. I n the two examples previously
Pard6ns 128.1975 128.0134
142.2176 142.0134 considered this doublet separation is
156.2378 156.0134 36.4 X mass units. The hydro-
170.2579 170.0134 carbon contributions are zero because
etc. etc. in both cases the hydrocarbon was of
the C,H2, type.
128.1611
142.1812
156.2013
127.9770
141.9770
155.9770
Figure 4 shows these two contribu-
tions in the general case. .?, is the
-
170.2214 169.9770 separation of the peak from the cor- M A S S DEFECT

etc. etc. responding hydrocarbon, and B is the Figure 4. Components of a mass

contribution from the hydrocarbon. defect

Table IV. Mass Numbers for Different Values of n and m

m
n 2nf2 2n+1 3n 2n-1 2n-2 2n-3 2n-4 2n-5 2n-6 2n-7 2n-8 2n-9 2n-102n-11
2 30 29 28 27 26 25 24
3 44 43 42 41 40 39 38 37 36 35 34 33 32 31
4 58 57 56 55 54 53 52 51 50 49 48 47 46 45
5 72 71 70 69 68 67 66 65 64 63 62 61 60 59
6 86 85 84 83 82 81 80 79 78 77 76 75 74 73
7 100 99 98 97 96 95 94 93 92 91 90 89 88 87
8 114 113 112 111 110 109 108 107 106 105 104 103 102 101
9 128 127 126 125 124 123 122 121 120 119 118 117 116 115
10 142 141 140 139 138 137 136 135 134 133 132 131 130 129
11 156 155 154 153 152 151 150 149 148 147 146 145 144 143
12 170 169 168 167 166 165 164 163 162 161 160 159 158 157
13 184 183 182 181 180 179 178 177 176 175 174 173 172 171
14 198 197 196 195 194 193 192 191 190 189 188 187 186 185
15 212 211 210 209 208 207 206 205 204 203 202 20 1 200 199
16 226 225 224 223 222 221 220 219 218 217 216 215 214 213
17 25% 239 238 237 236 235 234 233 232 231 230 229 228 227
18 254 253 252 251 250 249 248 247 246 245 244 243 242 241
19 268 267 266 265 264 263 262 26 1 260 259 258 257 256 255
20 282 281 280 279 278 277 276 275 274 273 272 271 270 269
21 296 295 294 293 292 29 1 290 289 288 287 286 285 284 283
22 310 309 308 307 306 305 304 303 302 30 1 300 299 298 297
23 324 323 322 321 320 319 318 317 316 315 314 313 312 311
24 338 337 336 335 334 333 332 331 330 329 328 327 326 325
25 352 351 350 349 348 347 346 345 344 343 342 34 1 340 339
26 366 365 364 363 362 361 360 359 358 357 356 355 354 353
27 380 379 378 377 376 375 374 373 372 371 370 369 368 367
28 394 393 392 391 390 389 388 387 386 385 384 383 382 381
29 108 40 7 406 40.5 404 403 402 40 1 400 399 398 397 396 395
30 422 421 420 419 418 417 416 415 414 413 412 411 410 409
31 436 435 434 433 432 431 430 429 428 427 426 425 424 423
32 450 449 448 447 446 445 444 443 442 44 1 440 439 438 437
33 464 463 462 46 1 460 459 458 457 456 455 454 453 452 451
34 478 477 476 475 474 473 472 471 470 469 468 467 466 465
35 192 49 1 490 489 488 487 486 485 484 483 482 48 1 480 479
36 j06 505 504 503 502 50 1 500 499 498 497 496 495 494 493
37 5 20 519 518 .5 17 516 515 514 5 13 512 511 510 509 508 507
38 ,534 533 532 531 530 529 528 527 526 525 524 523 522 521
39 548 547 546 545 544 543 542 541 540 539 538 537 536 535
40 562 561 560 ,559 558 557 556 555 554 553 552 551 550 549
41 576 ,575 574 573 572 571 570 569 568 567 566 565 564 563
42 590 589 588 587 586 585 584 583 582 581 580 579 578 577
43 GO4 603 602 60 1 600 599 598 597 596 595 594 593 592 591
44 618 617 616 615 614 613 612 611 610 609 608 607 606 605
4 .i 632 631 630 629 628 627 626 625 624 623 622 621 620 619
46 646 64.5 644 643 642 64 1 640 639 638 637 636 635 634 633
47 660 659 658 657 656 655 654 653 652 651 650 649 648 647
48 674 673 672 671 670 669 668 667 666 665 664 663 662 661
49 688 687 686 685 684 683 682 681 680 679 678 677 676 675
50 702 70 1 700 699 698 697 696 695 694 693 692 691 690 689

2148 ANALYTICAL CHEMISTRY

 Table V. Mass Defects o f Hydrocarbon Ions CnHznt2 t o C,HZ,,-~I
m
Molecular 2n+2 2n+ 1 2n 2n - 1 2n-2 2 n - 3 2 n - 4 2n- 5 2 n - 6 2 n - 7 2 n - 8 2 n - 9 2 n - 10 2n - 11
formula Mass units x 103
~ _ _ _ _ _ _ _ _ _ _ ~~

C'Z,H, -13.4 -6.7 0.0 6.7 13.4 20.1 26.8 33.5 40.2 46.9 53.6 60.3 67.0 73.7
C"C'2n-iHm-1 -8.9 -2.2 4.5 11.2 17.9 24.6 31.3 38.0 44.7 51.4 58.1 64.8 71.5 78.2
C18zC12n-zHm-z -4.5 2.2 8.9 15.6 22.3 28.9 35.6 42.4 49.1 55.8 62.5 69.2 75.9 82.6
C1%C'2,~Hm-a 0.0 6.7 13.4 20.1 26.8 33.5 40.2 46.9 53.6 60.3 67.0 73.7 80.4 87.1
C131C12n-4Hm--4 4.4 11.1 17.8 24.5 31.2 37.9 44.6 51.3 58.0 64.7 71.4 78.1 84.8 91.5
2
~ n + 6
_ 2 n_+ 5 2
_ n + 4 _2 n +_3 - ~
-15.6
-17.9 -11.2
-20.1 -13.4 -6.7
- 2 2 . 4 -15.7 -9.0 -2.3

Table VI. Mass Defects of Ions C,-lHm,O

m
Molecular 2n + 2 2 n + 1 2n 2n -1 2n -2 2n - 3 2n - 4 2n - 5 2n - 6 2n -7 2n -8 2n -9 2n - 10 2n - 11
formula Mass units x 108
C",-i H - 4 0 23.0 29.7 36.4 43.1 49.8 56.5 63.2 69.9 76.6 83.3 90.0 96.7 103.4 110.1
Ci3cizn-2Hm--50 27.4 34.1 40.8 46.5 54.2 60.9 67.6 74.3 81.0 87.7 94.4 101.1 107.8 114.5
C'3zC12n-3Hm-~0 31.!3 38.5 45.3 52.0 58.7 65.4 72.1 78.8 85.5 92.2 98.9 105.6 112.3 119.0
C'a~C1zn-aHm-,O 36.4 43.1 49.8 56.5 63.2 69.9 76.6 83.3 90.0 96.7 103.4 110.1 116.8 123.5
C''IC'~~,H~-,O 40.8 46.5 54.2 60.9 67.6 74.3 81.0 87.7 94.4 101.1 107.8 116.5 121.2 127.9
2n +6 2-
n + 5 2 n + 4 2-
n+3 ~
20.7
18.5 25.2
16.3 23.0 29.7
14.0 20.7 27.4 34.1

Advantages of the CHz Mass Scale. same nominal masses, are compared.
T h e chief advantage of using a mass I n these examples the mass defects for Table VII. Contributions t o Mass De-
scale based on CH2 = 14.0000 is that all the naphthalenes are the same, and fects b y Elements in Combination with
the number of precise masses to be obviously different from those for Carbon a n d Hydrogen"
calculated, stored, and compared with paraffins or ketones. Ions having one Defect for
data from a sample is very greatly less hydrogen atom than each of the m. = 2n.
reduced. examples given have mass defects (Aillimais
A further advantage of the CH, mass which are larger by 0.0067. They there- Element Formula of ion units)
scale is that the identiiication of ions is fore give sets of values similar to those Deuterium C,H,nD 1.55
simplified. As shown in Table 111, all presented in Table 111. Phosphorus Cn-3HL6P -13.1
Nitrogen Cn-1Hrn-2N 12.5
ions in a homologous series have the Oxygen C, IH,- cO 36.4
same mass defect. Ions having masses Sulfur-32 Cn-zHm-sS3' 90.5
MASS DEFECT TABLES
14 units apart and hztving similar de- Sulfur-34 C,iHrn-l$334 110.3
fects could be assumed to have similar I t will be appreciated that the data in Fluorine C,-zH+ F,F -37.5
Chlorine-35 C,-,H,, 1C13' 23.3
structures and to ditrer only in the Table I11 on naphthalenes, paraffins, Chlorine-37 C,-;H& ;Cla7 41 9
number of CH2 units. Averaging these and ketones would be better expressed Silicon C,H,Si 54.3
defects gives a more a x u r a t e value for in terms of the defects-Le., naphtha- a The defects may occur EM multiples or
comparison with the tables, lenes, 0.0804, paraffins, -0.0134, and combinations of those listed, and may also
Still another advantage of the CH2 ketones 0.0230. The negative defect be combined with the doublet C12 - H12
scale is that the same defects apply in of paraffin parent peaks is an exception = 93.8 millimass units.
the higher mass ranges. -4bove about to the general rule.
500 mass units the defects calculated do The most useful way of having these
not cover all of the ~ossiblecombina- data available would be in the form of
tions of atoms, but f,hey do cover a tables each of which would relate to a cases of ions formed n-hen several
proportion. The proportion covered particular kind of molecular formula- hydrogen atoms are stripped off the
decreases with increasing mass number, e.g., the formula C,H,, where (2n 2 ) + paraffins, olefins, and cycloparaffins.
but those combinations not included Q m Q (272 - 11) would cover the parent X paraffin with 14 hydrogen atoms
are unlikely combinations with large peaks of all the simpler hydrocarbons stripped off is indistinguishable from a
numbers of carbon ato n s and relatively including paraffins, olefins. cyclo- naphthalene of the same carbon number,
few hydrogen atoms. paraffins, akylbenzenes, styrenes, tetra- and the defects for paraffin ions with
An example of the . d u e of the CH2 l i s , and indanes and indenes. For a between 14 and 28 missing hydrogen
mass scale is given in Table I11 in given mass number, the values of n and atoms may be found, therefore, from the
which the masses of wries of paraffins, m may be obtained from Table IT7. table of defects for the parent and
alkyl naphthalenes, and aliphatic ke- The same molecular formula with a fragment peaks of naphthalenes and
tones, which have parent peaks a t the lower value of m would cover most other condensed aromatics. To pre-

VOL. 35, NO. 13, DECEMBER 1963 0 2149

 Table VIII. Mass Defects for Basic Combinations of Carbon, Hydrogen, Sulfur, Nitrogen, and Oxygen
Mass Mass Mass
defect defect defect
x 103 Formula x 10' Formula x 10'
<o.o 100.0-109.9 156.5
-81.3 101.7 156.9
-57.4 102.8 157.9
-45.0 103.0 158.6
-32.5 105.7 159.1
-21.1 105.7 159.8
-20.0 106.3 159.8
-8.6 106.8
-7.5 107.0 160.0-169.9
-3.3 109.1 160.2
0.0-9.9 160.9
110.0-119.9 160.9
0.0 110.2 161.9
3.9 110.3 163.2
9.1 112.1 163.2
114.2 164.2
10.0-19.9 115.4 164.3
12.5 118.2 164.9
15.3 118.2 166,5
16.4 118.8 167.6
16.5 119.4 168.3
169.0
20.0-29.9 120.0-129.9
21.6 170.0-179.9
120.7
24.9 121.6 170.4
27.8 122.2 171.6
28.8 122.6 172.3
29.0 122.8 172.3
123.5 174.2
30.0-39.9 123.5 174.4
33.0 124.5 175.6
34.1 125.6 175.7
36.4 126.7 176.3
37.5 126.8 176.7
126.8 176.7
40.049.9 127.9 177.6
40.2 178.4
41.5 130.0-139.9 179.0
45.5 179.7
130.1
46.6 130.7
48.8 131.2 180.0-189.9
49.9 131.9 180.0
134.0 180.8
50.0-59.9 134.7 180.9
51.6 135.3 183.0
52.7 135.9 184.1
52.9 136.0 184.4
53.9 137.0 184.8
58.0 138.1 184.8
138.7 186.7
60.0-69.9 139.3 187.6
61.3 139.3 188.1
64.1 188.1
65.3 140.0-149.9 188.8
66.4 140.0
69.4 140.4 190.0-199.9
70.0-79.9 142.1 190.0
142.1 191.5
70.4 142.6 192.2
72.7 143.3 192.8
73.8 143.7 193.4
76.6 144.4 194.1
77.8 145.1 195.5
145.4 196.2
80.0-89.9 146.5 196.2
81.8 146.7 196.6
82.9 147.7 196.8
85.2 148.4 197.4
86.3 148.4 199.2
87.1 199.5
89.2 150.0-159.9 199.5
90.0-99.9 150.5 200.0-209.9
151.8
90.3 151.8 200.1
90.5 152.5 200.6
93.8 154.6 200.6
94.3 154.6 200.8
97.6 155.1 202.5
99.6 155.8 202.9
~~

2150 ANALYTICAL CHEMISTRY

 Table VIII. Mass IDefects for Basic Combinations of Carbon, Hydrogen, Sulfur, Nitrogen, and Oxygen (continued)
Mass Mass Mass
defect defect defect
x 103 F xmula x 103 Formula x 103 Formula
204.0 246.3 293.0
204.1 246.9 293.3
204.6 248.4 293.3
205.9 248.4 293.9
206.5 248.9 294.4
208.0 249.6 294.4
208.7 294.6
208.7 250.0-259.9 296.4
209.2 250.3 296.7
209.9 297.8
250.3 297.9
210.0-219.0 250.7 298.4
251.7 299.7
210.6 252.4
212.0 253,O 300.0-309.9
212.0 253.6 300.4
212.6 253.6 301.8
212.7 254.0 302.5
213.3 254.7 302.5
213.9 254.7 303.0
213 9 255.7 303.7
215.0 257.0 304.4
215.4 257.0 305.8
216.0 25s. 1 305.8
216.4 258.1 306.4
216.6 258.7 306.5
217.3 307.0
217.3 260.0-269.9 307.7
218.4 307.8
219.0 260.3
219.4 261.4 308.8
262.1 309.2
220.0-229.9 262.8 309.8
220.5 262.8 310.0-319.9
220.6 264,2 310.3
220.6 265.4 310.4
221.7 266.1 311.1
222.3 266.1 311.1
223.1 266.8 312.2
2'24.0 268.0 312.8
224 5 268.2
269.5 313.2
224 5 314.3
225.0 269.5
314.4
225 7 314.4
226 4 270.C-279.9
315.5
226.4 270.1 316.2
227,8 270.5 316.9
22s 5 270.5 317.8
229.1 271.4 318.3
229 7 272.2 318.3
229, S 272.8 318.8
273.5 319.5
230 0-239 9 273.8
230 4 274.6 320.0-329.9
230 s 274.7 320.2
231 9 276.8 320.2
232 5 277.9 321.6
232 5 278.1 322.3
233 1 278.6 322.9
233 1 278.6 323.6
233 8 323.6
234 2 280.0-289.9 324.2
234.9 280.5 324.6
235.9 281.4 325.7
235 9 281.9 326.3
236.5 281.9 326.4
237.1 282.6 326.9
237.5 283.9 326.9
238 2 288.3 327.6
238.9 286.0 328.0
238.9 286.6 328.6
239.3 286.6 329.7
287.2 329.7
240.0-249.9
240.3 287.9 330.0-339.9
240.5 289.3 330.3
241.6 290.0-299.9 330.9
242.2 331.3
242.2 290.0 332.0
242.9 290.0 332.7
244.3 290.4 332.7
245.6 290.5 333.0
245.6 291.2 (continu:ed)

VOL. 35, NO. 13, DECEMBER 1963 2151

 Table VIII. Mass Defects for Basic Combination of Carbon, Hydrogen, Sulfur, Nitrogen, and Oxygen (continued)
Mass Mass Mass
defect defect, defect
x 103 Formula x 103 Formula x 103
334.1 380.0-389.9 420.7
334.3 420.7
335.4 380.4 421.4
336.0 380.5 421.8
336.0 381.0 422.5
336.7 381.7 423.5
338.3 383.1 424.1
339.4 383.8 424.7
339.4 383.8 425.1
384.2 425.8
384.4 426,5
340.0-349.9 385.0
386.8 426.5
340.1 387.1 426.8
340.7 387.1 427.9
342.2 387.7 428.1
342.2 388.2 429,2
342.7 388.2 429,8
343.4 388,4 429.8
344.1
344.1 390.0-399.9 430.0-439.9
344.4 430.5
345.5 390.1
346.2 390.5 431.9
346.8 391.6 433.2
347,4 391.7 433.3
347,4 392.2 433.9
347,8 393.5 434.6
348.5 394.2 436.0
348,5 395.6 436.0
349,5 396.3 436.5
396.3 437.2
396.8 437.9
350.0-359.9 397.5 437.9
398.2 438.2
350.8 399.6 439.3
350.8 399.6
351.9 440.0-449.9
351.9 400.0-409.9
352.6 440.0
354.1 400.2 440.6
355.2 400.3 441.2
355.9 400.9 441.2
356.6 401.5 441.6
356.6 401,6 442.3
358.0 402.6 442.3
359.2 403.0 443.3
359.9 403.7 444.6
359 I 9 404.1 444.6
404.2 445.7
404.9 445.7
360.0-369.9 404.9 446.4
406.0 447.9
360.6 106.7
361.9 449.0
407.0 449.7
362.0 408.1
363.3 408.2
363.3 450.0-459.9
408,2
364.0 409.3 450.4
364.3 450.4
364,4 410.0-419.9 451.8
365,2 453.0
366.1 410,O
410.7 453.7
366.6 453.7
367.3 411.6
412.1 454.4
367,6 455.7
368.4 412.1
412,6 455.8
368.5 457.1
413.3
413.5 457.1
370 0-379.9 414.0 457.8
414.0 458. 1
370.6 415.4 458.2
371.7 416.1 459.0
371.9 416.7 459.9
372.4 417.4
372 4 417.4 460.0-469.9
374 3 418.1
3i5 2 460.4
375.7 418.4 461.1
375.7 119.5 461.4
376.4 462.2
420.0-429.9 462.3
377.7
379.1 420.2 464.4
379.8 420.2 465.5

21 52 ANALYTICAL CHEMISTRY
 Table VIII. Mass Defects for Basic Combinations of Carbon, H y d r o g e n Sulfur, Nitrogen, a n d O x y g e n (continued)
Mass Mass Mass
defect defect defect
x 103 1'0 rniula x 103 x 103 Formula
465.7 498.7 532.0
466.2 499.8 533.8
466.2 535.0
468.1 500.0-509.9 535.0
469.0 500.5 536.1
469.5 500.8 536.1
469.5 501.9 537.1
502.0 538.4
470.0-479.9 502.0 539.5
470.2 503.1 540.0-549.9
471. 5 503.8
472.9 504.5 540.2
473.6 505.9 543.5
474.3 505.9 544.2
474.3 507.1 544,2
474.8 507.3 547.5
475,s 507.8 547.5
476.9 507.8 548.3
477.6 509.9 549.5
477.6 550.0-559.9
478.0 510.0-519.9
478.2 510.5 550.9
478. 8 511.2 551.6
511.2 562.8
480.0-489.9 511.9 553.7
512,2 554.9
480.6
480.9 513,3 560.0-56Ll. 0
480.9 514.0
482.0 514.0 560.0
482.2 514.5 561.9
482, 8 514.5 564.0
483.9 515.2 565.3
484.3 516.3 568.1
485.5 517.3 568 1
486.0 518.5 569.3
487,3 519.6
570.0-579 9
488.0
489.4 520.0-529.9 571 4
520.3 572.6
490.0-499.9 520.3 574.4
490.1 521.9 580.0-589.9
490.1 523.6
523.6 581.8
490.6 583.9
491.3 525,3
525.7 585.8
492.0 587.9
493.4 527.0
527.7 589.1
493.4
494.1 528.4
529.8 590.0-599.9
494.7
495,3 529.8 594.3
495.4 598.3
496.4 530.0-539 9
497.5 531.0 600.0-609.9
498.0 531.7 601.6
498.6 531 7 605,7

serve the values of n and TIL as those example, the ions containing one oxygen 177 lies in the range from (2n + 2 ) to
obtained from Table .V, the empirical atom and having a nominal mass of (an - 11). Below these are the defects
formula for naphthilenes may be 128 would have the empirical formula for the first four isotope peaks which
written as Cn+1H,-12, where m = C,-IHm-40 where m is again equal to could occur a t the same mass number.
2% + 2, instead of t'ie usual formula (2n + 2). Substituting an oxygen atom for a
CnH2n--12. It will be seen from Table Peaks from ions containing one C13 carbon and four hydrogen atoms will
IV that for a mass number of 128, n = atom can only be resolved from the give a peak at the same mass number,
+
9 and m = 2n 2 = 20. The formula normal hydrocarbon peak a t the same but a mass defect which is larger by
thus gives the usual formula; CI0H8. nominal mass when the mass number is 36.4 millimass units, the spacing of the
The number n might b ? described as the fairly low (below about 50). Further doublet CH4-0. Thus, for the molec-
"equivalent carbon number" because instrumental developments will, how- ular formula C,,-lHm-40 we have a
it is in fact the number of carbon atoms ever, make it necessary to distinguish table similar to Table V, but with each
in the simplest hydromrbon ion which betneen these peaks and precise masses entry increased by 36.4 millimais units
could be found at a particular mass of the ions will be required. Provision (Table VI). Similar tables can he pre-
number. has been made for these data in the pared for other empirical formulas
Ions containing oxygen, nitrogen, or tahles. involving oxygen, nitrogen, sulfur, etc.
sulfur can have their molecular formulas Table V gives the mass defects of the I n practice, Table V is the basic table
expressed in a similar manner; for ions n i t h the formulas Cnl*Hm, where and the subsidiary tables are prepared

VOL. 35, NO. 13, DECEMBER 1963 2153

Table IX. Mass Defects of Some Table x. Assignment of Masses on the CH2 Scale
Combinations of Elements with Phos- Analvsis of defect
phorus" H"
Maas defect Mass contri-
form = 2n Precise defect bution R.esidud
Formula (millimaas units) mam
Mass (CH2 =
-13.1 No. 14.000) units) n m units) units) Assignment"
80.7
-0.6 351
352
350.8402
351.8469
159.8 25 2n ++1 -6.7 166.5 CzrHa~Oz
11.9 153.1 25 2n 2 -13.4 166.5 CZ,HI2O2
24.4 353 352.8535 146.5 26 2n - 11 73.7 72.8 C,,H*,O,
36.9 354 353.8602 139.8 26 2n - 10 67.0 72.8
23.3 365 364.8402 159.8 26 2n + 1 -6.7 166.5
59.7 366 365.8469 153.1 26 +
2% 2 -13.4 166.5
96.1 367 366.8535 146.5 27 2n - 11 73.7 72.8
132.5 368 367.8602 139.8 27 2n - 10 67.0 72.8
77.4 369 368.8624 137.6 27 2n - 9 64.8 72.8 _ _ ~ ~- _ -
2n - 8
~

167.9 370 369.8647 135.3 27 62.5 72.8 Ci1zCi2zzHz~0~

258.4 379
380
378.8402
379.8469
159.8
153.1
27
27
2n
2n
++1
2
-6.7
-13.4
166.5
166.5
C&:6Oz
CZsH36Oz
348.9
66.6 381 380.8535 146.5 28 2n - 11 73.7 72.8 C2eH,,Oz
103.0
139.4 a Residual defects of 166.5 and 72.8 millimass units corres ond to the formulas
175.8 Cn-lH,-zoO~ and Cn-zH,-aO~, respectively. (See Table VIII.) fIence for n = 25 and
212.2 m = 2n +1, we have CP4HP102, etc.
These mass defects can be added to
those for combinations listed in the previ-
ous tables.
sidual corresponding to one of the
formulas in Table VIII. This formula Table XI. Comparison of Residuals
is a general molecular formula for the with Calculated Residuals from Part
by adding to each defect a mass defect unknown ion. It may be converted into of the Mass Spectrum of 4,4-bis-Methyl-
which is the spacing of the doublet a specific formula by substituting the ene (2,6Ditertiarybutyl Phenol)
formed by the peak with which we are appropriate values of n and m. M~ units
S x 103
concerned and the simple hydrocarbon The mass measurements given in Re- Residual
ion. Table X are hypothetical and contain Maas sidual (calcu-
To avoid listing in full each of the no errors in measurement. The cal- No. (found) lated) Bssignment
tables of defects, Tables VII, VIII, and culated residuals and the residuals en- 351 159.9 166.5
IX have been prepared in which the countered in actual measurements have 352 158.3 166.5
general formula of the combination of been compared in Table XI. The 353 67.5 72.8
atoms and the appropriate doublet 354 72.9 72.8
measurements were made with a Con- 365 190.2 166.5
spacing h a r e been listed. Table VI1 solidated CEC 21-110 spectrometer 366 186.9 166.5
lists formulas and defects involving one using photographic detection. 367 84.4 72.8 C1;H;;O;
atom of deuterium, phosphorus, nitro- 368 82.3 72.8 CzsH8aOz
gen, oxygen, sulfur-32, sulfur-34, 369 68.3 72.8 CiaCi2z~Hos0,
CONCLUSIONS 370 63.1 72.8 C13zC'2zaH:s0~
fluorine, chlorine-35, and chlorine-37. 379 183.4 166.5 C26H5602
I n Table VI11 the same information is The main advantages of the CH2 380 173.3 166.5 CtaH3e.O~
given for combinations of oxygen, scale can be summarized as follows. 381 78.1 72.8 C&a7Oz
nitrogen, and sulfur rrith the limitations A reduction by a factor of about 30
on the numbers of these atoms which times in the amount of data to be cal-
were discussed previously. Table IX culated, stored, and subsequently com- (6) Craig, R. D., Errqck, G. A., Waldron,
liits similar data for a number of pared with precise mass determinations. J. D., "Advances in Mass Spectrom-
combinations involving phosphorus. The mass defects found from high res- etry " Pergamon Press, London, 1959.
The formulas and defects in Tables olution spectra can be compared (7) Mattauch, J., Phys. Rev. 50, 617
(1936).
VII, VIII, and IX may be added to- directly and associated peaks can be ( 8 ) Ibad., p. 1089.
gether in cases of more complicated recognized immediately. (9) Mattauch, J., Herzog, R., 2. Phys.
formulas. 89, 786 (1934).
Application of the Tables. An (10) Nier, A. O., Natl. Bur. Standards Proc.
LITERATURE CITED 522, 29 (1953).
example of t h e use of t h e tables in t h e (11) Nier, A. O., Roberts, T. R., Phys.
interpretation of precise mass measure- (1) Beynon, J. H., "Mass Spectrometry Rev. 81, 507 (1951).
ments is given in Table X. This table and its Application to Organic Chem- (12) Nier, A. O., Roberts, T. R., Franklin,
istry," Elsevier, New York, 1960. E. G., Ibid., 75, 346 (1949).
shows the initial separation of the pre- (2) Beynon, J. H., Williams, A. E., (13) Voorhies, H. G. Robinson, C. F.,
cise mass into a mass number with its i'Maas and Abundance Tables for Use Hall, L. G., Boubafrer, W. M., Berry,
corresponding n and m values, and a in Mass Spectrometry,'' Elsevier, New C. F$ "Advances in Maas Spectrom-
mass defect (mass number - precise York (in press). etry, Pergamon Press, London, 1959.
(3) Carlson, E. G., Paulison, G. T., Hunt,
mass). R. H., O'Neal, M. J., ANAL.CHEM.32,
The hydrocarbon ion with the same 1489 (1960). . RECEIVED for review April 24, 1963.
value of m has a mass defect (found (4) Collins, T. L., Johnson, W. H., Nier, Accepted August 12, 1963. Presented at
A. O., Phys. Rev. 94, 398 (1954). the meeting of Committee E 1 4 on Maas
from Table V) which is listed in the (5) Craig,.R. D., Errock, G. A. "Ad- Spectrometry of the American Society for
sixth column. Subtracting this defect vances in M W ~Spectrometry," Per- Testing Materials, San Francisco, Calif.,
from the observed defect gives a re- gamon Press, London, 1959. May 19-24, 1963.

2154 0 ANALYTICAL CHEMISTRY