played in chemical analysis by microwave spectroscopy remains to be determined. To this end, it is important that those in the business of chemical analysis become sufficiently familiar with the technique to recognize when microwave spectroscopy can be applied profitably to their problems. ACKNOWLEDGMENT
One of us (VWL)would like to thank the National Science Foundation for financial support. LITERATURE CITED
(1) Aleksandrov, A. N., Rysovskiy, G. E., Zh. Anal. Khim., 22, 1532 (1967). (2) Beaudet, R. A:, Ph.D. Dissertation,
Harvard University, Cambridge, Mass.
(3) Curl, R. F., Jr., J . Mol. Spectrosc., 29, 375 (1969). (4) Dailey, B. P., “Physical Methods of
Chemical Analysis,” W. G. Berl Ed. Vol. 111, Academic Press, New kork, N.Y., 1956, pp 281-301. (5) D y q s , A., Dijkerman, H. A,, Zij erveld J. Chem. Phus.. 32. 717 “
I
I
(1960). ’ (6) Esbitt, A. S., Wilson, E. B., Jr., Rev. Sci. Znstrum., 34,901 (1963). (7) Flygare, W. H., Ann. Rev. Phys. Chem., 18, 325 (1967). (8) Funkhouser, J. T., Armstrong, S., Harrington. H. W.. ANAL.CAEM..40 ( l l ) , 22A (1968). ’ (9) Goldstein, J. H., “Treatise on Ana-
lytical Chemistry,” I. M. Kolthoff and P. J. Elving Ed., Part I, Vol. 5, Wiley, New York, h.Y., 1964, pp 3233-3238.
(10) Gordy, W., Cook, R. L., “Micro-
wave Molecular Spectra,” Wiley-Interscience, New York, N.Y., 1970. (11) Gwinn, W. D., Luntz, A. C., Sederholm, C. H.; Milliken, R., J . Comput. Phys., 2, 439 (1968). (12) Hanington, H. W., J . C h . Phys.,
46,3698 (1967). (13) Zbid 49,3023 (1968). (14) H a A g t o n , H. W., Heern, J. R., Rauskolb, R. F., HewbtCPackard J . 22 (lo), 2 (1971). (15) Hilderbrandt, R. L., J . Chem. Phys., 51,1654 (1969). (16) Hironaka, Y., Hirota, K., Hirota, E., Tetmhedmn Lett., 1W6, 2437. (17) .Hirota, K., Hironaka, Y., Hirota, E., am.,1964,1645. (18) Hrubesh, L. W., UCRL Report 73197 resented at the Jomt Conference dn% easurement of Environmental Pollutants, Palo Alto, Calif., 1971. (19) Hughes, R. H., Ann. N . Y . A d . Sci., 55, 872 (1952). (20) Jones, G. E., Beers, E. T., ANAL. CHEM.,43, 656 (1971). (21) Kim, H., Gwinn, W. D., Tetrahedron Lett. 1964,2535. (22) Ifneubuehl, F., Gaeumann, T., Guenthard, H. H., J . Mol Spectrosc., 3, 349 (1959). (23) Lide, D. R., Jr., Sum. Prog. Chem., 5,95 (1969). (24) Lide, D. R., Jr., Advan. Anal. Chem. Instrum., 5,235 (1966). (25) Lide D. R., Jr., “Encyclopdia of
Industhal Chermcal Analysis, F. D. Snell Ed., Vol. 11, Wiley, New York, N. g., 1966, pp 600-611. (26) Laurie V. W., Aceounts Chem. Res.,
3,321 /lain\ (27) 1 1963,1472. (28) Morino, Y., Hirota, E., Ann. Rev. Phys. Chem., 20, 139 (1969). (29) Momo, Y . , Hirota, E., Nippon Kagaku Zmshi, 85,535 (1964).
(30) Rmehart, E., Physics Department University of Wyoming, unpublished
work.
(31) Rudolph, H. D., Ann. &. Phys. Chem., 21,73 (1970). (32) Schafpen, L. H., Curl R. F., Jr Sympos~~m on Molecular f!itructure ana Spectroscopy, C o b b u s , Ohio, 1969, paper U13. (33) Scharpen, L. H., J . A w . Chem. SOC.,(in press). (34) Scharpen, L. H., Rauskolb R.,
Tolman, C., submitted to Anal. 6hem.
(35) Scharpen, L. H., Pittsburgh Confer-
ence on Analytical Chemist and ~ p p l i e dSpectroscopy, Clevelanz ohia, 1971, paper 39. (36) Sugden, T. M., Kenney, C. N;< Microwave Spectroscop of Gases, Van Nostrand, London, 1565. (37) Starck, B., “Molecular Constants from Microwave Spectrosco yl,LandoltErnstein [N.S.] Group PI, Vol. 4, Springer, Berlin, 1967. (38) Starck, B., Sektion Structurdocumentation, Universitat Ulm, Herman-Herder-Strasse 3, Westbau, 78 Freiburg, West Germany. (3:) Townes, C. H., Schawlow, A. L., Microwave Spectroscopy,” McGrawHill, New York, N.Y., 1955. (40) Thompson, H. B., J . Chem. Phys., 47,3407 (1967). (41) White, W. F.,.NASA, Langley, pri-
vate communication.
(42) White, W. F. presented at the Societ for Applied Spectroscopy Meeting. d w Orleans. La.. 1970. (43)-White, W. F.,’Chk. Eng. Progr., 63, 62 (1966). (44)Wilson, E. B., Jr., Science, 162, 59 (1968). (45) Wollrab, J. E. “Rotatiy,nal Spectra
and Molecular Qtructure, Academic Press, New York, N.Y., 1967.
Mossbauer Spectrometry lohn G. Stevens, Chemistry Department, University of North Carolina at Asheville, Asheville, N.C. 2880 I John C. Travis and lames R. DeVoe, National Bureau of Standards, Washington, D.C. 20234
T
is the fourth in a biennial series of reviews on Mossbauer Spectrometry, with the last one appearing in 1970 by DeVoe and Spijkerman, page 366R. The number of publications has continued to rise, but the rate of increase has sagged with this edition. The literature on li%n has continued to gain on the 67Fe publications in a trend dating back a t least to the beginning of this series. The popularity ranking of other isotopes, judged by the number of publications, has shifted somewhat. %lEu has retained prominence, but lroI,MIDy, and lSTe have s d e r e d declines. l*Au and 1%b have outstripped l*OI and UlDy in papers published, and 99Ru climbed ahead of 6iNi. The increases HIS REVIEW
in InAu, IWb, and 99Ru are the more notable due to an overall decline in the “other isotope” papers. Even so, the frontiers of Mossbauer spectrometry have been extended by observation of the effect for the first time in iWm (664,W m and ls*Sm (9?‘),W u (SI$), 1OlRu (689)and relW(769). The first velocity spectrum has also been recorded for mlHg (7W). Figure 1 shows the status of the Mossbauer spectrometry of the elements. It should be emphasized that for many of these measurements, low temperature is required. Increasing maturity is evident in a variety of aspects of Mossbauer spectrometry. Instrumental rarities of the past, such as wide-range temperature control, superconducting solenoids, and
S84R * ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
absolute velocity calibration, are becoming commonplace. Vital juices once invested in equipment develop ment have been diverted to betterresearched interpretations. Purely experimental papers simply tabulating observed parameters and offering tenuous hypotheses are declining rapidly in the “Fe literature, although less rapidly for lloSn. Theoretical sophistication widely employed in data interpretation is discussed under “Structure and Bonding” below. The fruits of instrumental advancement are evidenced in the same section and in the discussion on “Applications.” Publications are increasingly more “material-oriented” than “technique-
L T t f E w&3SBAUER EFFECT HAS BEEN OBSERVE0
Figure 1. Periodic table of the Miissbouer isotopes, showing the number of isotopes (lower left corner) and nuclear transitions (upper right corner) for each element exhibiting the Miirsbauer effect (non-shaded). Adapted from the Mossbauer Effed Data lndex [663lwith slight modiflcation. (Used by permission.)
oriented.” Inferences from M h b a u e r data are commonly compared with inference drawn from other experimental techniques. Of particdar note are some recent studies utilizing direct correlation between M h b a u e r parameters and those of other technioues such as X-ray emisaion spectmseopy (YO), NQR (741). . . .. NMR (6611. . EPR W6\. and photoelectron spectroscopy (E’SCAj (102). A parallel comparison of M 6 m bauerspectrometry with NMR (228) has been written as well. Another mark of maturity is the continued growth of studies in “hostile realms.” The grawing biological involvement attests to the willingness and ability to cope with isotopic enrichment, long accumulation times, and resolved paramagnetic hyperline interactions. Weak signal problem m y also be encountered when the M h bauer nuclide is employed as a probe by doping, or exchange into molecular sieves or ion exchange resins, when thio f i b are studied, or in frozeu Bolution or matrix isolation problem. The “MOW bauer probe” techniques above also evoke broadened peaks and/or multiple pattern due to clustering or other struetural environmental distribution factors. Equally complex s i p b often arise from studies of frozen solutions, glease~, chemical kinetics, electron rearrsngeI.
ment following electron capture, Burface adeorption, Domaion producta, terrestrial and lunar minerals, and complexes having the M h b a u e r isotope in two or more sites and/or oxidation s t a h . It is apparent from the literature that computer program for the m l u t i o n of complex spectra are being widely utilized. Literature referenm for a number of such program were given in a previous review in t h k seriea in 1870. The thin film studies alluded to earlier are part of an increasing proprtion of the M h b a u e r literature devoted to magnetic interactions. Thin film (and microparticle) studiea yield information about the thickness (diameter) of film (psrtiele) required to support magnetic ordering. Magnetic structure Studies are discussed under “structure and Bonding” below. The decline in the rate of incresse in publications has remained constant for the past three years, but there have been indicatora of the present scientificeconomic recession. One paper d e scribes a velocity drive b a d upon an inexpensive model airplane engine (676)! Practical applications with short ra economic potential are discussed in t e “Applications” section below. Alloy studies lead the field in this category, followed by analytical applications to c o m i o n products, o w , and other
$“
minerals. Of course, a completely new application during the past two years bas been the analysis of lunar samples. Studies of important catalysts, though s d in number, must not be overlooked in this category. A number of articlea of a review (490, 663), or introductory nature (166,166, 308, 330, 617) appeared on M h b a u e r spectrometry in general, and also on a wide variety of specialized s u b - c a h gories. T h e e ranged from such areas as chemistry (261); biology (170,38d,383, 4% 440); m e u u r g y (SW,406); solid state chemistry (396,384) and physics (69);molecular compounds (696); and lattice dynamica (3’7, 70, 110, 668); to such specific items 84 “Go, “Fe, and “%n as impurities in a h l i halides (650); a survey of data (66); “Fe and “%n substitutedirungameta (468); and studies of heme proteins (442). The middle ground includes tin applications (61); tin organics (662,770); high pressure (347); chemical bonding (618);quantitativeanalysis (631); glasseg (491,764); ~urface phenomena (336, 673, 677); lanthanides (236‘); and chemical aftereffects of nuclear resotiom (89,734). A series of reviews appear in Phys. Bull, 21, June (1970). Nioe tutorial and review articles a p pear in an introductory M6ssbauer spectrometry textbook edited by L. M a y
ANALYTICAL CHEMISTRY, VOL 44, NO. 5. APRIL 1972
3815 R
(491). Three other books devoted entirely to Miissbauer spectrometry were conference proceedings, including Volumes 5 and 6 of the “Mossbauer Effect Methodology” series, edited by I. G r u v e m n (308,304), and “Applications of the MiSssbauer Effect,” edited by I. Dezsi (184). The latter volume, comprising over 800 pages, contains a significantportion of the 1971 papers, including several of the above reviews. Two volumes of the “Miissbauer Effect Data Index,” edited by J. G. and V. E. Stevens (66$,663),covering the 1969 and 1970 literature, respectiveIy, have a p peared as well. These volumes constitute a most comprehensive bibliography for all aspects of the MBssbauer effect. The references in the tables and text of this review represent a selection of the chemical applications. The 1971 bibliography edited by one of us (John Stevens) is currently under way. The tabular emphasis of the previous two articles of this series has been retained this year, with a somewhat revised format. The tables provide an easily used reference which would be impossible with a purely textual account. Thus, the text is designed to emphasize
Table 1.
Isotopic abundance, % 0.0118 2.19 1.25 4.11 7.70 11.55 radioactive (ti/¶ 2.13 x 1@Y) 12.72 17.07 8.58 57.25 6.99 100 radioactive ( h z = 1.0 x 107~) 20.4 21.18 100
just a few areas that the authors deem to be of future importance while a t the
A key to the symbols listed in theae tables and the text is aa follows:
same time the authors apologize for any implied lack of foresight. The following three sections, “Instrumentation and P r o c e d m , ” ‘‘Recent Developments,” and “Theory,” provide some references not covered in the tables. The remainder of the text examines some of the trends mentioned above. Many of these trends are too pervasive to single out more than a few representative examples. The only cumulative information (drawing on work prior to 1970) in this article is contained in Table I. This table, showing the nuclear parameters appropriate to all of the Mossbauer transitions known to date, is included for the reader’s convenience, and is not intended to be definitive. Most of the values shown represent a subjectively weighted average of numerous experimental determinations extending over a period of years. The remaining tables deal with the chemical applications of Mossbauer spectrometry during 1970 and 1971 utilizing “Fe (Table 11), l%n (Table 111), and the other Mossbauer nuclides (Table IV)
ii
.
= fractional nuclear radius change
MSD = mean square displacement INSTRUMENTATION AND EXPERIMENTAL TECHNIQUE
Although little really new has occurred in instrumentation, many continuing developments are worthy of note. Stabilization is a popular theme in
4.20 97.7 8.8 5.2 9300 1.80 144
Magnetic moment of ground state, nm - 1.2980 +0.0904 +0.0904 -0.7487 +O .a756 -0.8788 -0.9672
Quadrupole Magnetic moment moment of excited of ground state, b state nm
+O: i55 +0.80 +0.43
...
-0:939 +3.2 -0.284
140.51 90 127.2 23.88 37.15 35.05 57.60
0.192 20.7 0.55 17.75 3.5 1.50 1.92
+5.6813 -0.623 -0.31 -1.0463 +3.3598 -0.8872 +2.8094
27.75 39.58 80.16 81.00
15.0 1.01 0.50 6.28
+2.0175 -0.7769 +O. 6908 +2.5791
+3:44
8.1 1.9 29.4 0.72
+4‘.’i30
+i:is
2.55 0.33 7.6
-0.8074
dioactive (ti/%= 10.7y) 12.29 100 145.2 8.30 07.25 72.50 radioactive (tils = 2 . 0 2 ~ ) 91.10 14.97 121.8 13.83 22.5 radioactive (tin = 93 y) 65.83 26.72 121.78
-
= quadrupole coupling constant line width = resonance effect magnitude = recoil free fraction = internal magnetic field = external magnetic field = asymmetry parameter = nuclear quadrupole moment = nuclear magnetic moment = ratio of the excited and ground state quadrupole momenta = ratio of the excited and ground state magnetic momenta = ratio of the excited and ground state nuclear g factors
Nuclear Parameters for Observed Mossbauer Transitionsa
state, nsec 29.4 14.41 136.32 07.40 93.31 67.03 9.40
= isomer shift = quadrupole splitting
A
20 1.42
-0.054 -0.054
2.58
-0.670 0
...
+0:72 +2.40 +0.60 +1.84 +2.84 $0.691
-0.06 0 0 0.13 +o. 18 -0.28 4-0.26
+O,iO
+0.3 20.05 -0.68 0 -0.26 0 -0.78
->0.’15
-0.55 0 0 -0.003 0
-0:319
-0.059 -0.25 -0.25
3.54 -0.44 -0.623
+0.7 -0.18 +0.060
+0:62
Quadrupole Total moment internal of excited conversion state, b coefficient
...
0
...
50
...
...
0.46
-0.05 -0.36 0.20 -0.70 -0.68
-0.41 -0.12
... ... ... ... ...
6.0 8.2 0.14 0.12 0.08 0.23 18 0.13 0.42 0.16 5.1 10.5 13.3 3.8 5.0, 15 2.1 1.74 110 0.47 6.1 4.9
0.6 -0.3
...
2.1 1.0 12
...
...
-1.8
1.3
(Continued)
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ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
Table 1. Nuclear Parameten for Observed M k b a u e r Transitionsa (Continued) Energy of QuadQudMiiasMagnetic Magnetic rupole rupole Total moment moment bauer Half life moment moment internal Isotopic transition, of excited of ground of excited of ground of excited convension keV abundance, % state, nm state, nsec state, nm state, b state, b coefficient radioactive 2 -0.04 35.84 +0.7 ... 0.30 (tils = 47 h) ~
22.71 47.82 52.18
2.15 14.73 20.47 15.68 24.87 21.90 100 2.29 18.88 25.53 28.18 100 1.56 33.41 22.94 27.07 14.88 100 3.03 14.31 21.82 31.84 12.73 97.41 5.20 18.50 27.14 35.24 99.99 0.14 26.41 14.40 30.64 28.41 62.93 1.64 13.3 16.1 37.3 62.7 33.8
81.99 21.55 83.36 97.43 103.18 123.14 60.02 86.54 105.32 88.98
64.0 79.51 75.3 58.0 86.79 25.65 43.84 74.57 80.7 73.39 94.70 91.5 80.56 79.32 79.80 79.3 8.42 84.26 66.74 75.89 78.67 76.5 82.1 113.81 88.36 112.97 93.2 93.33 6.21 136.25 103 100. 10 46.48 99.08 111.1 122.5 134.24 137.16 155.03 36.30 69.6 95.3 82.35 129.48 73.08 138.94 98.7 129.6 77.34 32.19 49.8
3.00 9.9 0.78 0.18 3.80 1.17 0.24 6.7 1.08 2.22 460 2.46 2.63 13 2.05 28.1 920 3.35 2.25 2.39 0.019 1.73 1.82 0.103 1.91 1.92 3.9 1.56 1.7 1.7 1.80 1.8 2.0 0.10 1.39 0.5 1.47 1.50
6800
0.040 1.2 1.37 0.179 0.832 1.26 1.01 0.01 0.840 0.710 0.50 1.64 0.30 3.8 0.094 6.3 0.071 0.170 0.620 1.91 >0.2 0.36
0
+3.464
+1.530 +1.530 +1.530 0 0.2576 0.2576 -0.2576
-
+o:& +2.58
+1.80 +3.21 +2.04 +O.%
...
-0.52
0
+0:786
-0.338
+o: k +0.63
0
0 +1.994 0 -0.472 -0.472 -0.472 0 0 +4.11 0 0 -0.565 0 0 -0.231 0 0.4918 0.4918
++
0 0 0
+2.230 0 +0.61
0 0 +2.35 +2.35
0 0
+O. 1172 +O. 1172 0 0 +3.204 0 0 +0.6558 +0.6558 +0.6558 +o. 1440 +o. 1440 +O. 1589 +0.1589 +0.6059 +0.6059 +o. 1449 -0.5566 0
+0:73 +0.566
-o:400 0.69 +0.69
...
0.70' -0.632 +0:636 0.638 +0.520 0.670 0.349 1.011 +O. 666 +0.674 +0.76 +1.8 0.53 +1.06
+0.64 +0.64 +5.22
...
+0:44 -0.62 +0.93 +0.59
+0.63 +0:562 f0.58 +0.23 0.977 +2o ,: +0.55 +0.470 0.72 -0.62
0 +1.14 +2.76 +2.76 +2.76 0 1.6 1.6 1.6 0 +2.0 0 0 +1.28 0 +2.36 +2.36 +2.36 0 0 +2.82
D
0 2.83 0 0 0
0 0 0 0 0 0 +5.68 0 +3 0 0 +3.9 +3.9 0 0
0 0 0 0 +2.6 0 0 +0.8
+0.8
+0.8 +1.5 +1.5 +1.5 +1.5
0 0 +0.59 0.50 0
-1.94 +1.5
...
... 0.52 ... +1.3
1.1 1.3
...
1.3 1.3
...
2.1 2.28
+1.36
...
-1.96
...
...
-1.3
...
...
...
-1.1
... ... ... ... ... ... ... ...
... ...
-1.89
...
... ... ... -1.61 ... -2 ... ...
-1.8 -1.8 0 -0.72
... 0
0'
3.7
... ...
100 +0:420 0 13.22 ... 0 '00. radioactive (ti/* = 3.24 x 104~) 84.20 41 1.98 2.7 0.0057 43.45 0.252 ... ... radioactive (tils = 2.4 45.3 x 107~) 0.232 ... 99.27 0.245 44.7 0 0'. -3.0 0.5 radioactive (h/%= 2.2 59.54 63 2.8 1.5 4.1 4.0 x 1W.Y) radioactive (tilt = 7370 84.00 2.34 +1.58 ... Y) If there is no sign preceding the numbers in the moment columns, to our knowledge they have not been measured.
...
...
...
...
... ...
a , .
...
a
...
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
5.05 29 6 0.41 1.8 1.20 9.2 0.49 0.25 4.1 7.4 5.9 9.2 10.1 5.4 2.5 5 0.65 6.2 10 8.6 4.2 7.2 5.3 14 7 325 6.7 11.2 8.7 9 10 8 2.3 5.2 3.0 4.6 5.0 45 1.9 3.5 3.97 9.0 4.3 2.75 1.72 2.35 1.25 0.84 80 8 6.7 12.4 3.0 6.5 2.3 6.9 1.76 3.7 60 260
...
... ...
660
1.16 0.30
387R
Table II. Chemical Applications of 67Fe Mkbauer Spectrometty (1 970-1 971) Subject or meteriala studied
Auoys
Renuvke
substance Al-Co-Fe-Ni AlFe AlFe: Al-Fe
Au-Fe Au-Fe-Pd Be-Fe Co-Fe Cr-Fe Cr-FeSb Cu-Fe-Ni Fe-Gs
Hint Hint
Effect of external magnetic field on ordering Study of atomic ordering Study of solid solubility of Fe in Al HintVI. temperature Study of Fed6 phase Induced mapetwm in dilute alloys Spin relmation 6, A, and Hint vs. time of annealing Effect of Co neighbors on 6 and Hint Decomposition study Stud of metastable phase 6 aniHint 6, A, and Hint us. composition 6
and Hint
6 and Hint
4 magnetic Fe sites 6, A, and Hintl spin ordering 6, A, and Hint 6
6
Fe-Ni. Fe-Ni (Fe~-,Nl,)sSnr, (Fel-,Co,)sSn~ Fe-N , Fe-Pu, Fe-U Fe-Pi Fe-PGRe-Rh Fe-Rh FeSn y Y
Metals
Lanthanide-Fe Armco steel Austenite Carbon steel Martensite Stainless steel Steel Ticonal Monolayer Thin layers Isotopic effects Calibration Miscellaneous
Biological
Inorganic
Basilar membrane in squirrel monkeys Ferritin Hemerythrin complexes Hemin Hemoglobin Lyophilized liver microsomes Metmyoglobin Nitrogenase proteins Scenedesmus and spinach ferredoxins Sulfur rotein Tetra p tenylporphin Undecapeptide of cytochrome c Vitamin B1, and related cobalamins Fe-As, Fe-Sb
Superparamagnetism of ferromagnetic particles Study of Invar alloys Hint us. temperature Quench-enhanced ordering effects Study of magnetic transformation Site population data 6, A, and Hint Band filling study
_-
Hint Hint
Spin-flip effect Data at T = 5 OK 6 and A 6, A, and Hint 6, A, and Hint Calibration of Mijssbauer spectrometer Magnetic properties of inequivalent iron atoms Hin; VI. temperature 6, A, and Hint Hint us. temperature Influence of plastic deformation Determination of amount of austenite in steel Kinetic study of carbide precipitation Effects of carbon concentration Hint
Backscattering studies Study of thermomagnetic treatment A and Hint Analysis by backscattering Study of magnetic ordering Study of relaxation effects Search for Effect of carbon impurity on calibration A and p Mossbauer cross-section determination Use of circularly and linearly polarized recoil-free gamma rays A in a-Fe f us. temperature Effect of impurities of All Si, Gal Ge Observation of vibrations in the basilar membrane Intensity VI. temperature 6 and A Spin-spin relaxation Investigation of charges of the electronic structure 2 high spin iron sites 6 and A us. tem rature Study of the ropof iron in nitrogen fixation Study of the mechanism of electron transfer A
Electron configuration information 6 and A 6 and A 6 and Hint 6 and Hint A
Magnetic ordering at 68 "K 2 Fe sites
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ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
Table II. Chemical Applications of 67FeMossbauer Spectromety (1 970-1 971) (Conthud)
Subject or meteriBl8 studied
Remarks
Substance
Reference
6, A, and Hint
cerbide FeFt FeF2, FeCoNiF6, MgJ?eF6, MgFetFe FeFa KFeFd RbFeFd BaFeFd KxFeFa KaFeFa, Na:FeFI, (NH4)rFeFa Fe(OtPFt)a, Fe(O2PCL)a FeClt 6Ht0 FeCl, FeCla 6H10 Fe(NHa)aClt CuFeCL, AgFeC14, T1FeC14 Pf?OCI FeOCl FeI!. 4Ht0 Halides I(;Fe(CN)a, NHbe(CN)6 K$e(CN)6.3HtO 3B[to,
Bragg angle scattering of Moesbauer gamma rays 61 A1 m d Hint 6, AI and Hint Iduence of particle size 6, A, and f lattice dynamica 61 A, and.Hint Observation of induced antiferromagnetism Thermal shift at the magnetic phase transition %Dimensional antiferromagnetic order at 137 OK Hint us. temperature 6, A, Hint, and q at 4.2 "K Determination of amounts of Fez+ and Fe'+ A us. pressure Q and A. Distorted octahedral Study of thermal decomposition Study of magnetic phases Spin-spin relaxation and Gol'danskii-Karyagin effect 6 and A us. temperature with and without HeXt Temperature dependence of spectra 6, A, and r Q, AI and Hint us. temperature Bonding information 3d-chargedensity model described Identification of low spin Fez+, high s in Fe+s Mossbauer study in the vicinity of t i e ferroelectric phase transition 6 and f us. temperature Characteristic temperatures A us. temperature shows change in crystalline state 6
f
dependence on single crystal orientation
A
Partial A +-
and A Sign of e*q Q
8
Hint08. temperature A u8. temperature
Hint
Cyanides FerOr aFe2Oa
Curie temperatures dand A Use of isotopic labeling Supported on silica gel and alumina.6, A, and Hint A calculations Effect of doped Li Superparamagnetism of ultrafine particles Ex lanation of temperature dependent Mdssbauer Xata Bragg angle scattering of Massbauer gamma rays Effect of Laue diffraction conditions on Mossbauer gamma rays Preparation from Fe(0H)a Superparamagnetism of ultrafine antiferromagnetic particles Thermal conversion of TFeOOH to aFerOp Thin films f
Effect of nonstoichiometry on Mossbauer spectra Challenges the Verwey model for FerO, Decomposition study 6 and Hint Mossbauer effect study below the Verwey temperature Diffusion line broadening at high temperatures Hint
BaF1304, KtFeO4, SrFeO4 Bi,Fe4Os FeB08 FerBOs CuFeO2 Ca,Fe~,04 CdFerO4, ZnFerOd FeCrl-.Fei04 MgCr104, ZnCr204
Hint
Study of the effect of dopping with Cr Mossbauer effectstudy near the Ne61 temperature A u8. temperature Magnetic structure information Identification of a new phase-CaFetOs Sign of e* Q Site popdation data Observation of a first order anti-ferroparamagnetic transition (Continued)
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
389R
Table 11.
Chemical Applications of 67FeMkbauer Spectrometry (1 970-1 971) (Contimd)
Subject or material8
studied Inorganic
Substance
Remarks H,nt D m c t observation of reorientation of antiferromagnetic axie 6 m d Hint Reorientation of the Fea+sdns Nee1 temperature
CuFet.0, DyFeO: EraFecOl, ErFeO:, YbFeO:, TbFeO, KFeOl MgFe,04, MnFesO, NaaFesOp Ni,Fe:-,04 u NaFeOFe,Ti06, FeTitOs ZnFet04 CoAll.oFe.104, ZnAll .pFe, 1 0 4 NiFe~,Al,04 C&Fer-,Al,Os BiFe0:-PbZrO: ctd?e7v:o,4 CaaFerSi:Ols, CaaesGe:Ol* Y:-,CazFe5-,Si,01~, Y:-s,C&.Fes CoZnFe4Os Co1-,Zn,Fe~04 NiFeCrs-,O, FeCr,-,Fe,Od
Reference
of Fe concentration Hint
6, A, and Hint I, A, and Hint
-2V.Olr
c Angular ordering of spins Hi.: I, A, and Hint 2 Fe*+sites I u8. temperature 6, A, and Hint VB. composition S in relaxation eel temperature 2 Fe sites Hint and site population data Investigation of superstructure ordering
J
Hint
Site population data Maasbauer spectra in the temperature range 22 to 700 OC Hint
So replaces Fe in the octahedral sites only Hint
NiFeCrO, a Fe(HC0,)r CdFe(C0)r FeCOs IGFe(CaO, 3H10 a FerN FePt, FeP, FeSP, FeaP, FeCoP, FeRuP, FeNiP, FeNbP FeRuP Fe:(P04)i.8Hs0 FeS4 FeS1+, Fe0.d FeCrB, NItFe&(NO )r * Ha0 Sulfides FeSO4 F&oc* 4&0 FeSO,. 7H.O
I , A, and Hint Relaxation Determination of Fe*++/Fea+ ratio Spin reorientation Local distortions Hintus. temperature Effect of microwave radiation A Wd Hint f va. temperature Study of rectangular hysteresis loop Study of &in films Corrosion study Oxidation films Hint
Single Fe site I and A Polarization experiment Study of phase transitions Relaxation effects near Ne61 temperature Thermal decomposition Determination of easy axis of magnetization I , A, and Hint I, A, and Hint Hintv8. temperzture Hint
I, A, and Hint Hint
A
I and A I and A
Vacancy distribution
A us. temperature. q efg parameters for single crystal
Thermal decomposition study Thermal decomposition study Line broadening Relaxation A
Organic
Olefin iron tetracarbonyls Pyridine and picoline complexes FeAaXS(BF4)*(X =.Cl, Br; A, = o-phenylene-bw (dmethylarsine) Phthalocyanine complexes 4,4'-bis(heptyloxy)azoxybenzene Tris(acetoacetaxulide)iron(III ) (CtHs )SFeCL-,Br, Fe(acackC1 . ,-
Observation of small polarons Electric charge distribution Thermal decomposition study I and A d and A correlated with MO calculations
Smectic phase of a liquid crystal A
I H.Xt
(Continued)
390R
ANALYTICAL CHEMISTRY, VOL. 44,NO. 5, APRIL 1972
~
Table II. Chemical Applications of brFe Mossbauer Spectrometry (1 970-1 971) (Continued)
Subject or materids
studied Organic
Substance Tris(monothio &diketoriato)-iron(II1) complexea FeCl (p-MeC1-CONI.NC)4 Fe (qvo.he)rClr ;;$xrdine) de complexes Thiosemicarbazide compounds Fe (Py)&lr F e P y MSCN 11, Fe(Py)rCl*, Fe(Py)J, FeCl(&d&etonate )I
Remarks 6 and A
Determination of sign of e*@ 6 and A VI. temperature Determination of sign of erqQ 6 and A 6 and A 6 and A A us. temperature
(606j
(9)
Haxt
Ha;
6 6 and A I
and
or
6
and A
6
and A
A and Hint
Gol'danskii-Karaya& effect 6 and A vs. temperature Preasure effects 6 and A 6 and A 6 and A
Structure information
Chelate complexes Fe(I1) low s in complexes 1,1'-Diacet yberrocene
Sources
CoFe304 Co(NH,)sCh KaFe(C~04)a a3Ht0, I4Fe(CtO4), KCOFa, KaCoFs Cr, Cu, Rh, Pd, Pt, Au 30 differentmetallic elements Co-Tn __ __
Fe-Al MgO Diamond
6 and A 6 and A
Partial 6 and A Smectic liquid Plated on surface Observation of Fer+ state only Fe'+ and Fea+ Relation between stabilized FeJ+ and lattice energy Single line source after do ing with 1%Li Stud of charge states for XiiTerentlyprepared samples 6 an8Hint us. temperature Observation of Fe*+and Fes+ Observation of Fer+ Changes states as a function of temperature Rh best source for 4.2 O K
f
6, A, and Hint MFe ( n , ~67Fe ) Effects of pressure A
Irradiation with electrons Observation of Fea+ and Fe*+ 6 and A Doped materials
Ag, Au, Cu AgCl AgCl, NaCl Al Al, Cr, Mn, Mo, Rh, Si, V, W AlCo, AlNi Al10S
Ar, Kr, Xe
Au
BA" all0ys CdS, ZnS CoNi, cu
Cu, Cu-Mn alloys Cu-Ni alloya GaSb, InSb, Ge GaAs, GaSb, In&, InP, InSb GaNic
InSb
Aftereffect of Auger ion Atomic diffusion Line broadening Identification of Fe sites Study of shot-cooled samples 6 us. temperature Identification of Fe4Al1, and solid solution components Effects of impurity
(638, 639)
Hint
Study of the effect of composition on the spin relaxation time 6 . Isolated Fe atoms Population of interstitial and substitutional sites 6 and A 8. Nonmetallic Fe 6 and A Ir
and A Effect of pressure 6
Hint
Hint VI. temperature, 6 Short range magnetic order about Fe Effect of "CO impurities in 111-V semiconductors Giant magnetic moment 6 and r 2 Fe charge states A
Study of spin-flop transition Hintus. temperature A and Hint
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
391 R
Table II. Chemical Applications of 67FeMossbauer Spectrometry (1 970-1 971) (Continued)
Subject or materials studied Doped materials
Frozen solutions
Substance Mo Ni Ni-Pd alloys Ni %, Pd-X, Pt-X alloys (X = transition or noble metal) Pd, Pd-Rh alloys Pd-Rh alloys Pt Si ThOs ZnS Fea Fe' +,Fea + Fe gels Fe in acetic acid Fe in H;SO, and Hi0 Fe in MeOH Fe(II1)-EDTA compounds FeCh FeClr, FeCL, Fe(NOa)s FeCl,, FeC104, Fe(NH4)t(SO4); FeCls +
hmarks Kondo effect 8, A, and Hiat us. temperature r us. temperature Evidence of impurity clustering 8 and A
Curie temperatures Hiat
f us. temperature Hiat a t T 0.91 f 0.35 nsec
Pt W
RQ
W&,woa, wc
W CeOsl
KiOsCle, I(rOs(CN)s Fe-Ir, Ni-Ir trans-Bis(tripheny1phosphine)iridium carbonyl chloride Halides Au-Mn 0 ~ 0 4 ,
Au-Sn Au-Hg Au-CU, Au-Ag AurCr AutTb Au Au KAuCl,, KAu(CN)r Halides, oxides, azides Halides, oxides, cyanides RAuCl, RAuCl, (R = organic ligand), PhaAuX (X - anion ligand) Pd-Fe Pt ThOt, ThN, ThCt, Th USb a-Np
Inorganic
spectrometer development. De Waard et al. (189) have suggested a circuit modification to avoid "conditionally stable" behavior in the common electromechanical feedback drive system. Miyajima (608) has employed crystal controlled digital circuits, and Gol'danskii et al. (971) have used a quartz oscillator and an optical sytem with diffraction gratings to achieve velocity stability. The optical system described by Cos-
Coulomb exited source RQ Coulomb excited source fi and Q
C) (r?
6, A, and Hint 6 and A
6 and Hint Variable pressure, 6 and Hint 6 us. composition Charge screening of impurities 6 us. composition Study of ordered and disordered alloys 6
Microcrystals f us. T 6 and A us. pressure 6 and A
ay)
(f-9
6 and A
Band filling study Effect of low temperature neutron irradiation Observation of effect Hint
2 Np sites, e'qQ and Gol'danskii-Karya-
gin effect
6
Hintus. concentration No magnetic ordering down to 4.2 OK
Sources
396R
(r')
> 96 f 9 psec
grove and Collins (149) is not utilized in velocity control, but provides absolute calibration simultaneously with spectral accumulation and allows nonlinearities to be corrected in the computer analysis of the data. Simultaneous calibration (by standard absorber) is also a forte of the computerized spectrometer with a double ended transducer described by Biran and Shoshani (75). Preston (687) has taken a unique approach to
ANALYTICAL CHEMISTRY, VOL. 44, NO. 5, APRIL 1972
velocity stability with an electromechanical system which requires no feedback control! Special purpose spectrometers have been described, for moving loads up to 500 grams (@I), and for fast (
