Anal. Chem. 1984, 56, 199R-212R

(11DD) Kettrup, A,; Stenner, H.; Weber, H. Ber.-Dtsch. Ges. Mlneraloel-

(12DD) Kolb, B. LaborPraxls 1982, 6, 156. (l3DD) Kolb, B. Chromatographla 1982, 15, 587. (14DD) Larsson, L. Anal. Chem. Symp. Ser. 1983, 13, 193. (15DD) Leggett, D. C. Report 1981, CRREL-SR-81-26; Order No. AD-

(16DD) Llebl. M.; Seeleltner, G. Mlit. Versuchssfn . Qaerungsgewerbe Wien

wlss . Kohlechem. 1982, 268.

A108345. NTIS from Gov. Rep. Announce. Index 1982, 82 , 1540. _ _

1982, 36. 81. (17DD) Ott, U.; Llardon, R. Flavour 81 Weurman Symp. 3rd 1981, 323. (18DD) Pausch, J. B.; McKalen, C. A. Rubber Chem. Technol. 1983, 56 ,

AAO. (19DD)- Safersteln, R.; Park, S. A. J. Forensic Scl. 1982, 27 , 484. (20DD) Sakane, Y.; Nltanda, T.; Shlmoda, M.; Osajlma, Y. Nlppon Shokuhln

Kogyo Gakkalshi 1983, 30, 108. (2100) Shaw, D. A.; Anderson, T. F. Ind. Eng. Chem. Fundam. 1983,22,

79. (22DD) Termonla, M.; De Meyer, A.; Wybauw, M.; Jacobs, H. J. High Reso-

/ut. Chromafogr. Chromafogr. Commun. 1982, 5, 377. (23DD) Varner, S. L.; Breder, C. V.; Fazio, T. J. Assoc. Off. Anal. Chem.

(23DD) Vlerke, W.; Gellert, J.; Teschke, R. Arch. Toxicol. 1982, 51, 91.

Sampllng

(IEE) DI Pasquale, 0.; Vallatl, A.; Capaccloli, T.; Galli, M. J. Chromafogr.

(2EE) Duenges, W.; Bode, J.; Hoffman, H.; Mueller, M.; Soitau, B. Proc. Int.

(3EE) Gauthler, M.; Pllon, R.; Kutschke, K. 0. J. Chromatogr. Scl. 1982, 20,

(4EE) Greter, J.; Staahle, 0. Anal. Chem. 1982, 54, 1646. (SEE) Grob, K. Jr., Comm. Eur. Communltles, 1982, Anal. Org. Mlcropolluf.

(6EE) Grob, K., Jr.; Mueller, R. J. Chromafogr. 1982, 244, 185. (7EE) Hlltunen, R.; Laakso, I.; Hovinen, S.; Derome, J. J. Chromafogr. 1982,

(BEE) Hlnshaw, J. V. Jr.; Felnstein, P. L. Am. Lab. 1983, Sept., 116. (9EE) Hlnshaw, J. V., Jr.; Yang, F. J. J. Hlgh Resolut. Chromatogr. Chroma-

(IOEE) Hosklka, Y. Anal. Chem. 1982, 54, 2433. (1 IEE) Jacobsson, S.; Berg, S. J. High Resoluf. Chromafogr. Chromafogr

(I2EE) Kovarich, E.; Munarl, F. J. High Resoluf. Chromafogr. Chromafogr.

(13EE) Pankow, J. F.; Asher, W. E.; Isabelle, L. M. Anal. Chem. 1983, 55 ,

(14EE) Proske, M. G.; Bender, M.; Schomburg, G.; Hueblnger. E. J. Chroma-

1983, 66, 1067.

1982, 243, 357.

Symp. Caplllary Chromafogr., 4th 1981, 765.

283.

Water, 57.

237, 41.

fogr. Commun. 1983. 6 , 554.

Commun. 1982, 5, 236.

Commun. 1982, 5 , 175.

1451.

fogr. 1982, 240, 95. (15EE) Schomburg, G. Proc. Int . Symp. Capillary Chromafogr., 4th 1981,

371. (16EE)- Schomburg, G.; Husmann, H.; Schulz, F. J. High Resolut. Chroma-

fogr. Chromatogr. Commun. 1982, 5 , 565.

(17EE) Spencer, H. J. J. Chromatogr. 1983, 260, 164. WEE) Yang, F. J. J. High Resoluf. Chromafogr. Chromafogr. Commun.

1983, 6 , 448.

Multldlmenslonal

(IFF) Bellabes, R.; Granger, R.; Vergnaud, J. M. Sep. Scl. Technol. 1982, 17, 1177.

(2FF) Broeteli. H.; Rletz, 0.; Sandqvist, S.; Berg, M.; Ehrsson, H. J. High Chromatogr. Chromatogr. Commun. 1982, 5 , 596.

(3FF) Herkner, K.; Swoboda, W. Roc. Int. Symp. Capillary Chromatogr ., 4th 1981, 429.

(4FF) Huber, J. F. K.; Kenndler, E.; Nyiry, W.; Oreans, M. J. Chromafogr. 1982, 247, 211.

(5FF) Mueller, F. Am. Lab. 1983, i 5 , 94. (6FF) Phillips, R. J.; Knauss, K. A,; Freeman, R. R. J. High Resoluf. Chro-

mafogr. Chromatogr. Commun. 1982, 5, 546. (7FF) Welton, B.; Goedert, M.; Lyons, T. Chromafogr. News/. 1981, 9 , 56.

Hlgh-Speed GC (IGG) Berezkln, V. G.; Mallk, A.; Gavrichev, V. S. J. High Resoluf. Chroma-

(2GG) Duarte, P. E.; McCoy, B. J. Sepf. Sei. Technol. 1982, 17, 879. (3GG) Jonker, R. J.; Poppe, H.; Huber, J. F. K. Anal. Chem. 1982, 54,

(4GG) Leclercq, P. A.; Scherpenzeel, G. J.; Vermeer, E. A. A.; Cramers, C.

(5GG) Schutjes, C. P. M.; Vermeer, E. A.; Rijks, J. A.; Cramers, C. A. J .

(6GG) Schutjes, C. P. M. Ph.D. Dissertation, Eindhoven University of Tech-

Vapor-Phase and Supercrttlcal-Fluld Chromatography

(1") Board, R.; McManiglll, D.; Weaver, H.; Gere, D. CHEMSA 1983. (2") Fleldsted, J. C.; Rlchter, B. E., Jackson, W. P.; Lee, M. L. J. Chroma-

togr. Chromatogr. Commun. 1983, 6, 388.

2447.

A. J. Chromafogr. 1982, 241, 61.

Chromatogr. 1982, 253, 1.

nology, 1983.

fogr..l983, 279, 423. (3") Fjeldsted, J. C.; Kong, R. C.; Lee, M. L. J. Chromafogr. 1983, 279,

AAP . .-. (4") Futrell, J. H.; Wahrhaftig, A. L.; Randall, L. G. Report 1982, EPA-

(5") Parcher, J. F. J. Chromatogr. Sci. 1983, 21 , 346. (6") Peaden, P. A.; Fjeldsted, J. C.; Lee, M. L., Springston, S. R..; Novotny,

(7") Randall, L. G., Bowman, L. M., Jr., Eds. Sep. Sci. Technol. 1981, 17,

(8") Randall, L. G. Chem. Eng. Supercrn. Fluid Cond. 1983, 477. (9") Shafer, K. H.; Griffiths, P. R. Anal. Chem. 1983, 55 , 1939. (10") Smith, R. D.; Fjeldsted, J. C.; Lee, M. L. J. Chromatogr. 1982, 247,

6OOf3-82-061; Order No. PB82-249178.

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No. 1.

231. (11iiH)- Smlth, R. D.; Felix, W. D.; Fjeldsted, J. C.; Lee, M. L. Anal. Chem.

(12") Wllsch, A.; Felst, R.; Schnelder, G. M. Fluid Phase Equlllb. 1983, IO, 1982, 54, 1883.

299.

Mossbauer Spectroscopy

John G. Stevens*

Department of Chemistry, University of North Carolina at Asheville, Asheville, North Carolina 28814-8467

Lawrence H. Bowen

Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204

Mbssbauer spectroscopy has just completed its 25th year. For this Analytical chemistry biannual review, it is the 10th in the series (20th year). Many of us have watched with great interest the development of this field of research. There are now nearly 20000 articles written by research groups from over 70 different countries. Approximately 1200 articles have been published during each of the last 10 years. To commemorate the 25th anniversary of the Mossbauer effect, Editors (Deutch, Kaufmann, and de Waard) published a special issue of Hy- perfine Interactions (76). After the Foreword written by R. L. Mossbauer, the volume contains the following chapters:

OO03-2700/84/0356-l99R$06.50/ 0

"Mossbauer Spectroscopy in Physical Metallurgy" (U. Gonser), "Mossbauer Spectroscopy in Magnetism" (J. Chappert), "The Impact of Mossbauer Spectroscopy on Chemistry" (T. C. Gibb), "The Understanding of Nuclear Structure Through Mossbauer Experiments" (L. Grodzins), "Mossbauer Spec- troscopy of Implanted Sources" (L. Niesen "Mossbauer Studies of Valence of Fluctuations (I. Nowik), "'&n Mossbauer Spectroscopy" (T. Katila and K. Riski), "Mossbauer Spec- troscopy with 191Jg31r" (F. E. Wagner), "Mossbauer Spec- troscopy with Actinide Elements" (W. Potzel, J. Moser and G. M. Kalvius), "Experimental Techniques for Conversion

109 R 0 1984 American Chemical Society

MOSSBAUER SPECTROSCOPY

Electron Mossbauer S ectroscopy" (J. A. Sawicki and B. D. Sawicki), and "Isomer lhift Reference Scales" (J. G. Stevens).

Included in this review for Analytical Chemistry are papers that have been received and surveyed by the Mossbauer Effect Data Center since the last one in the series (304). Conse- quently, the literature will include years 1981 through 1983. During this time there has been a dramatic increase in the number of papers being received from China. The trend noted in earlier reviews toward industrial applications of the Mossbauer effect has continued particularly as they relate to surface studies, catalysts, electrodeposits, zeolites, steel slags, and amorphous substances. Especially active research on amorphous metallic solids is evidenced by the upswing in publications related to that area. Little change in instru- mentation has been noted except in the use of the channeltron for detecting the Mossbauer radiations. Conversion electron Mossbauer spectroscopy continues to gain wide acceptance. There are more experiments using geometries different from the most common transmission geometry.

There has been only one new Mossbauer transition reported since 1979. This new transition is from manganese, an element that has not been used before in Mbssbauer s ectroscopy (285). The actual transition is the 126-keV y inq5Mn which has been Coulomb excited with 1.0-MeV protons. Although this particular element is of great interest to chemists, the difficulty of doing the experiment and the poor data obtained make it doubtful that there will be much future experimen- tation.

As has been characteristic of Mossbauer spectroscopy, the vast majority of the pa ers discuss investigations of the 57Fe

gap between these and the next most active isotope 151Eu, for which approximately 50 papers were published during the last 2 years. Other active isotopes which have a combined number of publications of a proximately 200 are in descending order: 126Te , , lZgI 121Sb, l9'%u, 161Dy, and 237Np. Mossbauer studies using B7Zn have increased during the past 2 years. To perform 67Zn Mossbauer spectroscopy special ap aratus and care are needed but with the encouraging corngination of its high resolution and strong interest in the element itself, researchers have had renewed interest in it.

As well as the special publication of Hyperfine Interactions mentioned at the beginning of this review, one other eneral

in Mossbauer Spectroscopy, Applications to Physics, Chem- istry and Biology", edited by B. V. Thosar and P. K. Iyengar is part of the Elsevier Scientific Publishing Company series on "Studies in Physical and Theoretical Chemistry" (311). This particular volume contains 16 chapters prepared by a large variety of experts in the field of Mossbauer spectroscopy.

During this reporting period the Proceedings of the Con- ference on the Applications of the Mossbauer Effect, from the international meetin held in Jaipur, India, in December

approximately 1000 pages and over 270 papers. The most recent international conference on Mossbauer spectroscopy was held in Alma Ata, USSR, this past fall. It was v e r y y l y attended because of international tensions that existe then. Many scientists were either prevented from attending or found making arrangements too difficult. It is always disappointing when governments actually prohibit or create unsurmountable barriers to scientific and personal exchanges among their citizens as was the case for this particular meeting.

It would have been nearly impossible to have put this review together if not for the facilities of the Mossbauer Effect Data Center. The Center continues to publish the Mossbauer Effect Reference and Data Journal ten times per year to keep re- searchers up to date on work and activities in the field. To assist in the collection, evaluation and dissemination of data and information, the Center continues to publish a series of specialist handbooks which cover topics such as minerals, corrosion studies, conversion electron Mossbauer spectroscopy, ion implantation, theory, ca"t"lzc)"t" surface studies, amorphous materials, instrumentation, I, Ikt'e, and 121Sb. The Center continues to provide assistance for many specialized infor- mation needs of Mossbauer researchers.

In the 25 years of Mossbauer spectroscopy over 1200 reviews have been published. One of the main reasons for this large number of reviews is the diversity of application problems to which the Mossbauer effect can be applied. Almost every one

200R ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984

isotope, followed by I1 P Sn. Typically, there is a fairly large

book has been written on Mossbauer spectroscopy: "A d vances

1981, has been publishe d (318). This large volume contains

of the reviews published during the last 2 years focuses on a specific application area. The reviews covering industrial applications include those on catalysts (147), coal (I 77,209, 2111, and amorphous metals (55,93,110,53). Other materials studies include ion implantation of alloys (188), phase analysis (335), and ternary superconductors (88). There have been two different reviews on certain aspects of semiconductors, one on chalcogenide vitreous semiconductors (287) and the other on laser annealing of semiconductors (171). Chemical systems reviewed include the spin crossover phenomenon (120), bioinorganics (314), intercalation compounds (128), organotin (253), and a aper on a specific area of organotin, thiosulfur in five-coodnated Sn(1V) (18). One interesting paper is a review of the history of the attempts to elucidate the structure of triiron dodecacarbonyl, Fe3(CO) 2. This is interesting be- cause of the many changes in unaerstanding and because Mossbauer spectroscopy has played a significant role in de- termining the structure for the species (75). Two very ex- tensive reviews have appeared on y-ray lasers (13,12). The f is t one of these is written by Baldwin and Solem (Los Alamos Laboratory) and Gol'danskii (USSR Academy of Sciences). Although an extensive amount of research is still taking place in the Soviet Union and the United States, and probably elsewhere, it is unlikely that there will be any further reports in the open scientific literature because of the military nature of this area of research. Other reviews have as topics high- pressure techniques (170), the published literature since 1975 on relaxation (123), solid-state chemistry (327), and chemistry (59). A general treatment for chemists using Mossbauer spectroscopy has also been published (305). A collection of useful data tables is in the most recent volume of the "CRC Handbook of Spectroscopy" (303).

INSTRUMENTATION Several papers report the use of microprocessors to control

Mossbauer spectrometers. These typically contain 1024 channels and have storage capacities of 1.6 X lo7 counts per channel. Benedetii and Fernandez (23) describe a fully pro-

ammable eight-bit microprocessor in which wave forms can r e selected as well as the frequencies of the drive. With the addition of an ADC, their unit can operate also as a PHA. De Grave et al. (69) describe the use of a microprocessor in which interferometric calibration is performed during the collection of the Mijssbauer spectroscopic data. In addition to collecting these data, the microprocessor is also able to perform curve fitting of the data. I t is possible to graphically display raw unfitted data on the terminal. An additional capability is that the data collected in the microprocessing unit can be trans- mitted to a large external main-frame computer for complex spectral data fitting.

Another microprocessor unit is described by Dai and others (65). Nolle et al. (236) designed a microprocessor-controlled spectrometer for thermal scanning Mossbauer spectroscopy. The system they describe is low cost and it sets up the tem- perature, takes up the spectra, and evaluates the ordering temperature from the sequence of measurements.

Two different papers describe the use of the Apple 11+ microcomputers with 48k of RAM. Sisson and Boolchand (298) report the use of the Apple I1 primarily for the analysis of Mossbauer spectra. The run time for a six-line iron spectra is 1 to 4 h. While this is considerably longer than the time on the main-frame computer, the actual wait time is ap- proximately the same. Several suggestions are given for shortening the run time to 20-60 min. Sundqvist and Wappling (307) also use the Apple I1 microcomputer for Mossbauer data acquisition. The microprocessors as reported in these papers decrease the cost of the Mossbauer spec- trometer and have several advantages over many spectrom- eters, particularly the increased counts per channel and the possibility of software selecting wave forms and frequencies for the drive unit. In the future there should be further improvements.

Most of the detector improvements for Mossbauer spec- troscopy have been those associated with conversion electron Mossbauer spectroscopy (CEMS). It is now quite easy to obtain such spectra at temperatures as low as liquid helium, primarily through the use of the channeltron. This new device offers great promise for Mossbauer spectroscopy. It is able to detect Mossbauer conversion electrons at low temperatures. Measurements at 4 K can be performed with relative ease

M~SSBAUER s p ~ c ~ ~ o s c o p ~

the normal electron background produced by the chamber walls. Rather than having the usual metal or alloy as the resonance material, this detector uses thin coatin of sodium ferrocyanide Na,Fe(CN)610HZ0 enriched with%Fe. Since sodium ferrocyanide is soluble in water, it is quite easy to prepare thin coatings of homogeneous composition. Using the detector, the investigators examined a number of different layer thicknesses and gas compositions. They have been able to obtain over 400% linea which, is a substantial improvement over most other resonance detectors.

During this reporting period no substantial improvements in either heaters or cryostats for Mljasbauer spectroscopy are found in the literature. Nikolaev and Potapov (232) report the only improvements in the experimental techniques for high-pressure experiments. In their paper they describe a comparatively uncomplicated high-pressure chamber which is capable of providing pressures up to 17 khar for tempera- tures in the range of 78-450 K. The area of the samples used is approximately 20 mm2; this is an improvement over most other high-pressure devices.

A general computer program for fitting Mhbauer spectra up to 24 Lorentzians using a minicomputer is described by Verhiest (328). It is written in Fortran and has been used on both PDP 11 and Vax 11 Digital computers. Typical run times are from minutes to several hours on a PDP 11/34. In another paper Cai (47) examines the problem of fitting corn lex spectra and suggests a modified Gauss-Newton method. &dical ly . they not only take the first approximation from the Taylor expansion but also add a correction term that is described in their paper. Another variation from the normal Gauss and/or Newton method(s) is suggested by Aramu et al. (7). They describe a procedure in which special weight distributions are introduced. By using rectangular or Gaussian distributions with proper widths they have been able to minimize the hy- periime parameter fluctuations and get better results from the Gaussian weights.

An alternative to the method of least squares has been developed by Urwank (329). The concept of a probation calculation is used to develop a method of self-consistent fit of experimental spectra. The advantages of the method are that it does not contain any solution ambiguities for suitable basis functions above the limit of resolution power and that it decouples the single problems (single peak fit) in a dynamic matter.

A transmission Mhbauer polarizer which can be attached to any standard Mhbauer spectrometer is described by Barb e t al. (26). They describe its use in an experimental ar- rangement where the same transmission geometry for the Mbbauer spectrum is used for the Malus curve correaponding to the different energies of the polarized y-ray. With such an apparatus, it is possible to investigate the magnetic structure of thick absorbers. Hirvonen et al. (230) examined the transmission of polarized y-rays in media with an isotropic nuclear resonance absorption. They note that the incidence polarized beam decomposes into two components which are attenuated differently.

In two recent papers of interest on the scattering a t Bragg reflections, Ti e t al. (322) report their study on V,Sn and Kashiwase et al. (253) theirs on KCI. In both of these papers the authors report they they have been able to place energy resolution between the elastic and inelastic scattering within 4 X eV. In the Ti paper measurements are reported as a function of temperature for two different orthogonal ori- entations of the crystal. The Kashiwase group reports that their experimental apparatus includes a position-sensitive

because of the compactness and high efficiency of the chan- neltron for detecting secondary electrons. M h h a u e r mea- surements that were difficult or impossible before are now possible.

The actual experimental setup usin the channeltron is

source are mounted into a small vacuum chamber which then is inserted into the cryogenetic liquid. The device does not call for any special Dewars with windows. Instead, only a container of the cryogenetic liquid is needed. Such devices have been used to obtain CEMS spectra for 5'Fe, "%n I lslE u, and lanW (278). In another paper Sawicki and others (279) describe this device at low temperatures using a 100-mCi source. They are able to obtain spectral intensities of up to 400% and counting rates of Zoo0 counta/s for 57Fe. Further descriptions on channeltrons are given hy Sato et al. (275) and Atkinson and Cranshaw (IO).

detectors are used include the technique of coating the% tector cone with MgO coating. This coating increases the efficiency by over a factor of 3. Nakagawa et al. (224) report on the use of a gas-flow proportional counter for studying depth elective CEMS. Mizui (206) used a film plastic scin- tillator for CEMS of %n at temperatures down to 78 K. Bressani et al. (42) compare plastic scintillators with sodium NaI(TI). They show that there is a much better performance from the plastic scintillators when there is a high rate of single puke transmissions. Several other proportional detectors used for CEMS include one described by Isozumi et al. (237) de- tailing a proportional detector g o d a t temperatures down to 77K. Sato (273) also describes a proportional y detector which is operative down to 77 K. Its isometric design allows it to count both scattered and transmission gammas a t the same time. A unique ring detector reported by Gaubman et al. (103) is able to count Rayleigh scattering from a MBsshauer ex- periment. The improvement in the counting rate in such a detector is a factor of 20.

Medvedeva et al. (200) describe a specially constructed low background proportional resonance counter for Mhshauer spectroscopic studies in which the detector is shielded from

quite simple because the channeltron, t i e abeorber, and the

Other improvements for CEMS in which proportional-

detector. Renard et al. (262) warn that for comoarisons between

Mosshauer spectra using a correlation link the technique of Aramu (8) is only practical when the effective thickness does not differ by more than 0.25. This is because the deviations from the correlation line can arise from thickness effects as well an from differences in the nature of the samples. Un- fortunately, this unually eliminates the possibility of discrim- ination between twn unknown samples.

Lung et al. (187) present tabular data and a simple pro. cedure for determining ideal ahsorher thicknesses. On the basis of the strrhantic theory of nuclear events Shgh

et al. (2971 show that the background contribution to the Mbsbauer absorption can he reduced by several orders of magnitude by using an AC dual Doppler modulation tech-

ANALYTICAL CEMISTRY. VOL. 56, NO. 5. APRIL 1984 * Z O l R

MOSSBAUER SPECTROSCOPY

nique. They describe an experimental arrangement using stainless steel which was used to demonstrate the results of their theory.

One of the most active applied research areas of Mossbauer spectroscopy in recent years has been cultivated through the use of the conversion electrons that result from the Mossbauer resonance. Scattering geometry is used in these experiments rather than the transmission geometry typical of almost all other Mossbauer spectroscopic measurements. This techni- que, usually called CEMS has been known for some time. It has only been during the last 4 to 5 years that a great variety of experiments have been reported.

One use for CEMS is to obtain magnetic and electronic information at various depths into the surface. This exper- iment is extremely difficult, so several groups have examined the problem very carefully. Staniek et al. (302) investigated the depth sensitivity of this technique by using experimental results obtained from a series of thin iron films. In their experiments they have been able to note changes in the hy- perfine fields of the surface layers and that these hyperfine fields are different from that of the bulk material.

In another paper, Itoh et al. (138) used a high-resolution electron spectrometer, necessary for most of the depth se- lective Mossbauer measurements, to obtain information at various depths. In this study they measured the ener y distributions of the 7.3-keV electrons emitted from a thin 5780 source covered with iron films of various thicknesses. From these distributions they have been able to derive the accurate weight coefficients for depth selective CEMS. The results compare quite favorably with the theoretical calculations. Smit and Van Stapele (299) propose an alternate method for obtaining depth selective Mossbauer spectra in which only a simple proportional counter is necessary. They report ex- perimental results with depth resolutions of about 20-30 nm. To obtain the depth selectivity, they removed thin layers from the sample and measured the conversion electron Mossbauer spectra. The layer spectra (that is, the Mossbauer spectra associated with the removed layers) are determined by cal- culating the number of electrons which originate for each layer and reach the surface of the sample. They apply their tech- nique to the examination of YIG films in which they report the change in magnetization as a function of the depth.

A spherical electrostatic electron spectrometer is described by Yang et al. (337). With their spectrometer they are able to obtain excellent spectra within 1 day or even within several hours by using a 50-100 mCi source. The signal to background ratio is often in excess of 800%. The instrument was used specifically to study the dependence of the magnetic hyperfine interactions as a function of depth from the surface into a bulk sample of Fez03 film. They are able to determine differences in the hyperfine field of less than 100 G, Le., 0.02%. Also, they are able to determine extremely small changes of the quadrupole interactions a t the surface of foils. With the capability that this instrument has for measuring such small changes in the Mossbauer parameters, a number of new problems can be examined.

Another scattering geometry that is sometimes used is associated with resonance detectors. The detectors have a selective sensitivity to resonance y-rays and, consequently, a unique resolution. Discriminating efficiency of resonance detectors is due to the fact that the resonant absorption effect is used in the detection process. Resonance absorbers, called converters, are actually placed inside the detector. These converters need to possess a high fraction of absorption without recoil energy loss. They should have a single-un- broaded absorption line, and the line should coincide with the emission line of the source. While the first two requirements can be satisfied easily, the third re uirement is quite difficult and can be practically met only inXgSn and 12Te Mossbauer spectroscopy. Irkaev et al. (136) describe an experimental setup which meets all the requirements for the resonance detector. To et the emitted y-ray to have the required frequency for aisorption by the converter, the source is given a specific Doppler velocity. Such a device is appropriate for any Mossbauer isotope.

THEORY Some theoretical results are discussed in other sections.

Most of the papers covered in this section deal with isomer shifts or quadrupole splittings, although a few papers dealing

202R ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984

with other topics are included. Concerning isomer shifts, Bansal and Shrivastava (15) estimate the nuclear radius change in 40K from Hartree-Fock calculations on KX halides. Lie and Taft (178) use the Xa method to estimate electron densities in the FeSf cluster and relate these to isomer shift calibrations for 57Fe. Parish (243) evaluates literature data on isomer shift and quadrupole coupling correlations with electron coflipation for the main group sequence l19Sn, lZISb lZ5Te, and I. Some revised correlation equations ard presented. Makariunas (192) evaluates electron ca ture data and reports new isomer shift calibrations for I and lZ9I. Varnek et al. (326) use CNDO calculations for SnC14 and some of its organic complexes to compare with isomer shift data and relate these results to the interactioin between organic ligand and tin. Hartmann and Rygavjl (122) use the X a method to calculate electron densities in tellurium compounds and show that their results give agreement with earlier esti- mates of the nuclear radius change for lZ5Te. Obara and Kashiwagi (239) report ab initio molecular orbital calculations for various iron(I1) porphyrin complexes and relate these to Mossbauer isomer shifts and quadrupole splittings.

Czyzek (64) discusses the distribution of electric field gradients in amorphous solids and reviews experimental data in terms of the unique information obtained from Mossbauer and NMR on local angular distributions as opposed to the radial distributions from XAFS measurements. Zimmermann and Doerfler (340) present a method for thicknesss correction of quadrupole splitting data on single crystals. Litterst et al. (185) derive an analytical solution for electric field gradient fluctuations in the case of jump diffusion in an octahedral cage.

Kohn and Lee (162) interpret low-temperature valence fluctuation phenomena on the basis of a quantum mechanical model and oint out the error of interpreting these effects by an assumettime dependence. Riseborough and Hanggi (263) analyze theoretically the Mossbauer spectra of particles un- dergoing surface diffusion on fiiite surfaces. Rad0 and Walker (257) interpret results on spontaneous magnetization of fer- romagnets as a function of distance from the surface and discuss the effects of surface anisotropy. M0rup (214) presents approximations for the reduction in magnetic field at low temperature observed due to microcrystallinity. He relates the observed magnetic splitting to the particle size and magnetic anisotropy. Knapp et al. (160) discuss the theoretical basis for the unusual double line Mossbauer spectra of proteins and their temperature variation. The dynamics of protein structure are emphasized.

RELAXATION An active area of research during these last 2 years has been

on the spin crossover transitions which occur in a number of Fe(I1) and Fe(II1) complexes. The spin transitions are the 5Tz + lAl and the 6Al + 2Tz. Burnett et al. (45) studied several series of Fe(I1) and Fe(II1) complexes of 2,2’-bi-2- imidazoline and other related ligands. As for many of the studies, they used magnetic susceptibility in addition to the Mossbauer spectroscopy measurements to determine at which temperature the spin crossover occurs. Kambara and Sasaki (150) report on a theoretical approach to Fe(I1) + Fe(II1) transitions that are induced by molecular distortion in com- plexes which have spin crossover for both Fe(I1) and Fe(II1). Another study includes the effect of low pressures (up to 150 barr) (202). In another theoretical study pressure-induced high spin-low spin transitions in compounds of Fe(II1) are described (272). The effect of metal dilution on the spin crossover behavior in (FexM1,(phen)2(NCS)2) (M = Mn, Co, Fe, Zn) was investigated by Ganguli et al. (99). They report that in the host lattice, when the ionic radius is less than that of ferrous iron, the amount of rest paramagnetism and the region well below the transition temperature increase with metal dilution, whereas in the host lattice with a radius less than the radius of Fez+, the residual dimagnetism in the region is well above the transition temperature decreases with metal dilution. These observations are interpreted quantitatively in terms of “negative” and “positive” local pressures which change the Fe-N bond length.

Konig et al. (163) report report an extremely sharp high spin-low spin transformation. They also note the simulta- neous change of the spin and the lattice characteristics in addition to the order-disorder phenomenon of the para- chlorate ion. An unusual spin transition which includes a

7p

MOSSBAUER SPECTROSCOPY

two-step spin conversion in the crossover region in the system [Fe(B-pic) ]Cl,(EtOH) is reported by Koppen et al. (166). Sasaki and Kambara (271) examine the effect of an induced magnetic field on high spin-low spin transitions in both ferrous and ferric compounds. In another paper, Konig et al. (164) note an anomalous behavior when there are differences in effective thickness. The explanation for this particular be- havior is that the Mbssbauer fractions of the two spin states of a spin crossover transition are not the same. Muller et al. (217) studied the effect of domains in the high spin-low spin transition in (dithiocyanato)bis(2,2’-bi-2-thiazoline)iron(II).

Examples of electron hopping include a report by Coey et al. (611, Litterst et al. (182), and Merrup and Topsere (215). Coey et al. give evidence for a spontaneous, thermally activated charge transfer in cronstedtite, an iron-rich 1:l layer of silicate. Litterst et al. calculate the effect on the Mossbauer spectra of tetrahedral cage hopping for 67Fe with correlated jumps of an axial electric field gradient. Marup and Topsere discuss slow electron hopping in 60-A particles of Fe30e

Shaitan and Rubin (288) describe a model of a Brownian oscillator with very strong attenuation for which the results agree well with experimental data. In another paper these later authors (288) describe their investigation of Mossbauer absorption in overly damp, harmonical bound particles which have Brownian motion. This kind of modeling is close to descriptions of a variety of different biological systems. With their model, they have been able to obtain excellent fits of experimental data. In another biological application, Knapp et al. (160) used Mossbauer spectroscopy to study protein dynamics. The spectra they obtained were analyzed by three Brownian oscillator modes which are able to account for the protein-specific motion. Two of the modes are extremely over-damped and a third mode has a diffusion-like character.

There continues to be considerable interest in the literature in spin relaxation. There are constant improvements in the analysis of the spectra. Cianchi et al. (58) used asymmetry to simplify the analysis in such a way that they only need to invert a 40 X 40 matrix rather than an 80 X 80 matrix, used in most other previous theories. In another paper Hoy et al. (133) evaluate the nonadiabatic, stochastic model on exper- imental data of the paramagnet ferrichrome A at temperatures down to 115 mK. They have determined that the dominant relaxation mechanism is the spin-spin interaction. Basically they obtained good theoretical fits to all their data.

Recently there have been a number of relaxation experi- ments in which the material is a glass substance. These include materials such as Ba0-2Ti02-2Fez0 (139), YFez and Fe16N&2B14Si8 (2341, DyAg (541, and Fe(NO& in water (333). Other studies include the nuclear motion in an octahedral change (184), spin-lattice relaxation in TmAlz (116), and slow electronic spin relaxation in high-spin hexakis(pyridine N- oxide)iron(II) perchlorate (48). Gol’danskii and Stukan (109) discuss tunneling chemical relaxation by using emission Mossbauer spectroscopy. An excellent paper published by Bonville (35) describes the most frequently encountered paramagnetic relaxation methods (phonons, conduction electrons, exchange, or dipolar interactions) in condensed matter.

CHEMICAL STUDIES (IRON) In addition to the specialized subjects of the other sections,

it is proper in a review for Analytical Chemistry to discuss chemical applications of Mossbauer spectroscopy. Many more papers have appeared than could possibly be mentioned here, however. As has been our custom, we have generally omitted those papers in which straightforward Mossbauer measure- ments in conjunction with other techniques have given useful structural information, and concentrated on those in which Mossbauer studies are the primary focus. Even so, the ref- erences discussed below must be considered incomplete and somewhat arbitrarily chosen.

Both electron spin resonance and Mossbauer spectroscopy were used by Beardwood et al. (21) to ident the one-electron

product of this 2Fe2S protein analogue has proven difficult to stabilize. Their 4 K Mossbauer spectra were obtained with external field and show the two irons in the trianion are antiferromagnetically coupled. Moura et al. (216) studied a 3Fe-3S cluster from a natural ferredoxin, also by ESR and Mossbauer techniques. Their main emphasis is on the con-

reduction product of FezSz[ (SCH2)zC6H40]z 5t . The reduction

version to 4Fe-4S clusters by chemical treatment. Spectra were also obtained in an external field to characterize the magnetic structure. English et al. (84) obtained Mossbauer spectra for a number of oxidized iron porphyrin complexes with differing axial coordination and find a marked change in Mossbauer parameters depending on the bridging atom, which they interpret as a change in site of oxidation from metal to ligand. Boso et al. (39) have studied the Mossbauer spectra of a synthetic iron(1V) porphyrin complex as function of temperature and externally applied magnetic field. They present a theoretical interpretation based on tight spin cou- pling. Pecoraro et al. (248) report Mossbauer studies on the pH dependence of Mossbauer spectra from ferric enterobactin. Although a variety of changes in the spectra were observed, the iron remained Fe(II1) in aqueous media. Reimer et al. (261) obtained low-temperature Mossbauer spectra in applied magnetic fields for carbonyl complexes of biddimethyl- glyoximato)iron(II). They find a large field gradient effect both cis and trans to the substitution when CO replaces amine as ligand.

Turning from biological systems and analogues to organo- metallics of nonbiological interest, we mention here several papers of interest. Muller et al. (218) discuss both absorption and emission spectra they obtain for square-planar complexes of Fe(I1) (the latter showing essentially no Mossbauer effect). They fiid rather low isomer shifts, presumed due to covalance. Neshvad et al. have reported a number of studies on ferrocene complexes. These include a study (227) of substituent effects on ferrocenyl-carbenium ions in which a decreasing quadru- pole splitting was correlated with increasing electron donation from the substituent Nicolini and Reiff (228) discuss magnetic interactions in the linear chain complexes M(2,2’- bpy)(.HzO)zSO,, where M is Fe, Ni, or Cu and bpy is bi- pyridine, both from low-temperature magnetic susceptibilities and, in the case of the iron compound, Mossbauer spectra. Blomquist et al. (30) compare their extended Huckel molecular orbital calculations with Mossbauer and ESCA results on iron dithiolate complexes. Mossbauer spectra at 4 K were also obtained in an external field to evaluate the sign of the field gradient. Moore et al. (213) report Mossbauer studies of mixed-metal bimetallic complexes of pentacyanoferrate(II), in particular with Co(II1) and Rh(II1). Some differences are observed in the remote effects from the two metal ions on Mossbauer spectra, but these do not appear to explain the photochemical behavior previously observed.

CHEMICAL STUDIES (TIN) Following the success of previous Mossbauer studies of

matrix-isolated atoms and small clusters, Shamai et al. (289) report a double Mossbauer experiment on matrix-isolated clusters of Fe-Sn. Using a special cell and both 57Fe and ll%n sources, they were able to detect all the dimers and most trimers of this mixed system. The Sn-Fe-Sn trimers were more abundant than FeSnz.

Korecz et al. (167) use isomer shifts and quadrupole splittings to determine coordination number and geometry in some 35 stannatrane complexes. They compare Mossbauer results with available X-ray, NMR, and IR data and find good agreement. Mahieu et al. (191) give results on some tetra- hedral organotin compounds containing the Sn-Mn bond. Changes of Mossbauer parameters with substitution of the organic groups are emphasized. A study of cis-octahedral complexes of SnX with urea and thiourea ligands was made by Calogero et al. (51). These complexes have no quadrupole splitting observed but exhibit a marked decrease in isomer shift from the original tin(1V) halides. The variation with temperature of the Mossbauer peak area indicates nonin- teracting, discrete molecules. Cusack et al. (63) use l19Sn Mossbauer effects as well as IR to characterize new inorganic tin derivatives of amino acids or esters. Cusack et al. (62) have also reported spectroscopic studies on crown ether complexes with SnC1, and SnBr,. Low isomer shifts are observed, con- sistent with strong complexation. The complexes with 18- crown-6 and 15-crown-5 exhibit appreciable quadrupole splitting, while those with 12-crown-4 have none. This is interpreted as due to cis-oxygen coordination for the latter.

CHEMICAL STUDIES (OTHER ISOTOPES) As example of the chemical information from the lzlSb

Mossbauer effect, the work of Pebler et al. on organoantimony

ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984 203R

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compounds shows marked difference between Mossbauer results for Me3Sb0 and Ph3SbS (247). The former has large negative quadrupole coupling constant, while the latter has almost zero. These authors also obtained the crystal structure of Ph3SbS and show that the tetrahedral arrangement about Sb agrees well with Mossbauer results. Dehe and Behn (73) used 121Sb(V) substituted in spinel oxides to study the 3u- per-transferred-hyperfine field. Double Mossbauer experi- ments indicate the magnetic ordering affects Sb at higher temperatures than Fe in the same spinel. Nagarathna et al. (222) report extended Huckel calculations on small clusters of Sb. These calculations are compared with Mossbauer re- sults on matrix isolated samples to refine the value of A( r 2 ) for 121Sb.

Matrix isolation studies are also reported for 151Eu by Montan0 (210). Magnetic field line broadening is observed for the isolated atoms. The methods for preparation of an- hydrous Eu13 are examined by lSIEu Mossbauer effect in the studies of Jenden and Lyle (144). None of the Eu(II1) iodide was observed after various treatments, which all gave Eu(I1). Double Mossbauer experiments with IS1Eu and 57Fe have been used to characterize the magnetic interactions in perovskites of formula E U F ~ ~ - ~ C ~ , O ~ by Gibb (1062. The observed su- pertransferred field at both 57Fe and IEu depends on the substituent, Cr, having certain unique characteristics. Gerard et al. (105) report an unusually large magnetic hyperfine field for lSIEu in EuFe4P12. This is interpreted as due to f-d band coupling. Other recent studies of Mtjssbauer-active rare-earth elements include papers by Friedt et al. (92) on lelDy in Dy(I1) and Dy(II1) halides and oxyhalides and a study on magnetic and electric field interactions in RzFe3Si5 compounds using lS5Gd, l@Er, and S7Fe Mossbauer spectra (Noakes et al., ref 235).

Concerning the actinide elements, reviews have been re- ported by Friedt (90) and by Potzel et al. (255). A review of 9 7 A ~ Mossbauer spectroscopy is given by Parish (244). A few

recent examples of application of lg7Au Mossbauer effect to chemical problems should be mentioned. Katada et al. (156) report results on mixed-valence compounds and chelates of Au(II1) with phenanthroline and related ligands. Evidence from the Mossbauer spectra is presented for metal-metal interaction in some of the com lexes studied. The effect of

plexes using lg7Au Mossbauer effect by Sakai et al. (268). Evidence of reduction of y-irradiation is presented for one of the Au(II1) complexes. Hill et al. (129) report lg7Au studies on thiolates and their phosphine complexes of Au(1). Their results are discussed in light of the biological role some of these complexes have as antiarthritic drugs.

The Mossbauer effect in 61Ni was used by Rummel et al. (267) to study the effect of Hz adsorption/desorption on LaNi,. Microprecipitates of nickel metal ap eared in the Mossbauer

given by Katila and Riski (157). Potzel et al. (256) re ort new measurements on the quadrupole interaction in &Zn and discuss the use of Zn metal for calibration of drive units.

Both lnI and l%e Mossbauer effects were used by Birchall et al. together with NMR data to characterize OTeF5- com- pounds (29). The relative electronegativities of OTeF6- and F- are discussed, the former being somewhat less electro- negative on the basis of Mossbauer results. Berry et al. (25) report iodine Mossbauer studies on PbIz and the mixed va- lence lead oxyiodide. In both cases the iodine spectra were characteristic of I-. Several recent studies on iodine-doped polyacetylene have appeared. Kaindl et al. (148) report both 1, and 15- linear groups observed, with 1, decreasing as the doping level increases. Matsuyama et al. (199) also find ev- idence for the presence of I- and discuss its importance in the conductivity behavior of the polymer.

y-irradiation has been studie B on several organogold com-

spectra after cycling. A review of 6: Zn Mossbauer effect is

PHASE TRANSITIONS AND HIGH-PRESSURE EXPERIMENTS

The Mossbauer effect is a useful technique to study changes in solid-state structure with temperature or pressure. Mag- netic phase transitions are particularly amenable to study by this technique. In addition to the abrupt changes in Mossbauer parameters at a phase transition, gradual effects of increasing pressure are of interest in a number of the papers surveyed.

Potzel et al. (254) report 67Zn Mossbauer spectra from ZnS

up to 33 kbar. Their main objective was to determine the effect of pressure on the isomer shift, and a linear increase of s-electron density at zinc was found. A substantial sec- ond-order Doppler shift correction was required for the very narrow 67Zn resonance. Kapitanov et al. (152) studied single crystals of a-Te02 up to 50 kbar in two orientations to de- termine the effect of pressure on the anisotropy of the re- coilless fraction. A reversal in anisotropy occurs at about 15 kbar. High-pressure lg7Au Mossbauer experiments are re- ported on the mixed valent CszAuzC1, and on CszAgAuC& and AuI by Stanek (301). In the former compound, the gold sites become crystallographically indistinguishable at about 50 kbar. However, Mossbauer results show the Au+ and Au3+ ions are distinct up to 68 kbar at 45 K. Abd-Elmeguid and Micklitz (1) studied the 151E~ Mossbauer resonance in EuMo6SB up to 16 kbar. They show that th.e superconductivity observed at p > 7 kbar is not due to a valence change in the Ed+. Ratner and Ron (260) applied uniaxial tensile stress on face-centered cubic stainless steels and determined the change in isomer shift as a function of stress.

Phase transitions in SnF2 have been studied by using the '19Sn Mossbauer effect by Birchall et al. (28). Sharp dis- continuities are observed at the first-order transition a - y at about 425 K. The second-order y - /3 transition has no discontinuities. Van Deen and Van der Woude (322) used Mossbauer spectroscopy to study the orderdisorder transition in Ni3Fe at 780 K and to map the phase diagram in this region. Single crystals of FeI, were studied in external fields up to 15 T by Calis et al. (49). The high-field magnetic transitions produce three different ferrimagnetic phases at low temper- ature. The exchange mechanism accounting for these tran- sitions is presented in terms of a model consisting of eight sublattices.

Dockum and Reiff (78) report Mossbauer studies of the reversible phase transition in bipyridyliron(I1) thiocyanate between 130 and 185 K. Unlike the high spin-low spin transition in the bis(bipyridyl)thiocyanate, the above transition involves no spin change, but a structural reorganization. Sato et al. (276) observed evidence of a second-order phase tran- sition near the melting point in acetyl and carboxyl ferrocenes. The Mossbauer line width and recoilless fraction exhibit anomalous behavior associated with the transition. De Grave et al. (71) studied the Morin transition in hematite containing about 5% Al. Below 245 K two magnetic phases coexist. The disappearance of the antiferromagnetic phase occurs gradually as the temperature is raised and is accompanied by spin re- orientation. Pure hematite has been studied up to 53 kbar by Bruzzone and Ingalls (43). They explain the changes in quadrupole splitting and hyperfine field observed at the pressure-induced Morin transition in terms of the anisotropy energy density.

DEFECTS Several studies have appeared on various aspects of the

Mossbauer spectroscopy of wustite, Fel-,O. Chalabov et al. (52) report decomposition studies in inert atmosphere and show that cation vacancy concentrations can be estimated from the Mossbauer spectra of the decomposition products. Gohy et al. (107) report room temperature Mossbauer spectra of Fel,O and Fel,,MnyO and analyze these in terms of two doublets and a singlet, the latter due to Fe3+. In an inde- pendent study, Hope et al. (131) used neutron diffraction, magnetic susceptibility, and Mossbauer effect to study Fel-,Fel-,-yMnyO. They interpret the Mossbauer data as indicating three doublets due to Fe2+. Both these papers indicate the relation of the measured spectra to the defect structure. Point defects in vanadium metal have been studied by Janot et al. (143) using both positron annihilation and Mossbauer s ectroscopy. The Mossbauer measurements were

unusually high for Mossbauer experiments. LATTICE DYNAMICS

The temperature dependence of the recoilless fraction gives information on the dynamic properties of solids. As in the past, a variety of papers have dealt with applications of this type of measurement. Litterst et al. (186) measured tem- perature variation of the Mossbauer resonance in vinyl- ferrocene polymers. The anomalous changes in recoilless fraction at temperatures from 80 K to 130 K are interpreted

made with 7p Co in V as source up to temperatures of 1700 "C,

204R ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984

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as due to hindered motion of the ferrocene grou Kandpal and Bhide (151) used diacetyl ferrocene as a Mossiauer probe to study molecular diffusion in nematic liquid crystals at low temperature. Several smectic liquid crystals containing tin in the crystalline matrix have been studied at 77 K by Ktorides et al. (169). Effects of the alignment angle on the lI9Sn re- coilless fraction are reported.

Molloy et al. (208) report variable-temperature '19Sn Mossbauer results on Sn(I1) and Sn(IV) amines. These results are interpreted in terms of structure. Arsenio et al. (9) present data on the temperature dependence of hyperfine field and recoilless fraction for single crystals of the linear chain com- pound RbFeS2. The results are compared to previous mea- surements on KFeSz. Shenoy et al. (291) have studied the superconducting LaFe4P12 by variable-temperature Mossbauer spectroscopy, as well as in external field. Their results are related to the superconducting properties. Mossbauer dif- fraction from sin le crystal lead germanate was used by Gavrilov et al. (1047 to investigate the lattice dynamics around its ferroelectric transition.

Rotenberg et al. (264) report recoilless fraction measure- ments on small particles of Fez03 imbedded in Teflon. The behavior of the Mossbauer fraction is related to the dynamic properties of the polymer matrix. Picone et al. (252) have measured hyperfine fields and recoilless fractions for ultrafiie metallic iron and iron oxide prepared in a variety of ways. The behavior of the Mossbauer fraction indicates that the mode of recoil depends on temperature and on the supporting material. Petry et al. (250) report emission Mossbauer ex- periments on electron-irradiated 57C0 in aluminum. The decrease in intensity around 15 K is correlated with localized diffusion of the 57Fe in an interstitial cage. High-temperature measurements of 5 7 C ~ in aluminum are reported as a function of crystal orientation by Mantl et al. (197). A theoretical interpretation of the diffusion process is given.

A number of studies have appeared in the last few years on protein dynamics in metmyoglobin and deoxymyoglobin. Krupyanskii et al. (168) used Rayleigh scattering of Mossbauer radiation to study motions in metmyoglobin samples with varying water content. Parak et al. (242) report Mossbauer absorption of 57Fe in deoxymyoglobin and on K,Fe(CN), dissolved in the water of metmyoglobin. The protein dynamics are correlated with water mobility in the system. Bauminger et al. (19) also re ort 57Fe absorption measurements in met- myoglobin and &oxymyoglobin and discuss their interpre- tation in terms of protein dynamics.

KINETIC STUDIES Some studies related to kinetic phenomena have been

discussed in previous sections. The use of Mossbauer spec- troscopy is generally to evaluate phase composition at various stages of reaction. Because of the length of time required for obtaining such spectra, the application of the technique to follow time dependent changes in situ has been limited. Nevertheless, Mossbauer measurements sometimes prove crucial to explaining kinetic results.

Phillips and Dumesic (251) report a Mossbauer study on the thermal decomposition of iron pentacarbonyl on Grafoil. In this paper the outgassing methods are emphasized. Kinetic measurements and Mossbauer results indicate an alteration of site reactivity with pretreatment. The interaction of NO with F e Y zeolite is reported by Segawa et al. (284). Infrared spectroscopy was used to follow the kinetics and Mossbauer spectroscopy to study the changes in iron sites.

Corrosion is a kinetic process particularly susceptible to Mossbauer study. Peev and Rousseva-Plachkova (249) com- pare kinetic data and Mossbauer results on the effect of rust transformers in preventing corrosion by formation of phos- phate layers. Belozerskii et al. (22) used depth selective CEMS to study the oxidation process on iron foils. The passivation effect of H20z is shown. Leidheiser and Music (175) report Mossbauer studies of long-term atmospheric oxidation of steel. The results indicate a predominant influence of sulfate on the corrosion products. Saragovi-Badler et al. (270) also studied long-term oxidation of steel in the atmosphere, but with em- phasis on the chan es in oxidation products due to CuS04 pretreatment. Domie and Kyvelos (79) used CEMS to study oxidation of a thin crystal of iron. The various oxide phases detected are related to the kinetics of the process. Some depth-selective resulta are reported. Other papers on oxidation

of iron surfaces are discussed under the section SURFACE STUDIES.

ENVIRONMENTAL MATERIALS Both naturally occurring and synthetic minerals continue

to be of wide-spread interest among Mossbauer spectroscop- ists. A number of papers have discussed results on goethite, a-FeOOH, and hematite, a-Fe203, which have been substituted by AI3+. Goodman and Lewis (114) have prepared a large number of samples with varying aluminum content up to -30% Al and report Mossbauer spectra at room temperature and 77 K. They emphasize the complications introduced in the spectra by the effects of substitution and small particle size. Johnston and Norrish report room temperature spectra of a series of natural goethites (146) and present evidence that other impurities in addition to A1 may have marked effect on the observed spectra. Murad (220) suggests that a distribution of magnetic fields may be used for such spectra to characterize the samples and presents data on a variety of samples both at room temperature and down to 4 K. Fysh and Clark (94) use the line width method to determine the recoilless fraction for pure and Al-substituted goethites at 4 K and room tem- perature. They find particle size to have little effect on low- temperature spectra. In contrast, Murad and Schwertmann (221) report a multiple correlation of magnetic field with both A1 content and degree of crystallinity at 4 K.

Fysh and Clark (95) also report recoilless fraction and magnetic field data for Al-substituted hematites at 4 K. They find marked differences between samples prepared at high temperature and those prepared at <600 "C. De Grave et al. (70) prepared hematites at -500 "C with up to 30% A1 and analyze the observed spectra in terms of a molecular field model. Tomov et al. (313) studied the effect of temperature on the formation of A1203-Fe203 solid solution, using Mossbauer spectroscopy as a probe. Reaction does not occur below 330 "C and a maximum of -10% A1 is incorporated by this technique.

Iida et al. (134) give an updated reported on their model for the electronic structure of magnetite, Fe304, emphasizing the Verwey transition and the population ratio of the two Fe(I1) sites. Fayek and Bahgat (86) show results on cobalt- substituted magnetite with a high degree of cobalt substitu- tion. Magnetic interactions are emphasized in their discussion. Gallagher et al. (97) used Mossbauer spectra to study the thermal decomposition of siderites, FeC03, both pure and impure samples being included. Both magnetite and iron metal are observed as products below 500 "C. Above that temperature wustite becomes prominent.

The magnetic ordering in sheet silicates is discussed in papers by Coey et al. (60,14). This ordering appears only at low-temperatures, C20 K, and for iron-rich samples. In the earlier study three 1:l layer minerals are reported, while in the second paper, example 2:l layer minerals are discussed.

Several groups report on studies of oxidation in chlorites. Kodama et al. (161) used bromine to produce oxidation and conversion to vermiculite. Before oxidation, two doublets for Fe2+ and one for Fe3+ were observed. After oxidation two Fe3+ doublets were found. No magnetic ordering appears in the original samples at 4 K. Borggaard et al. (38) subjected an iron-rich chlorite to air oxidation at 480 "C and subsequent reduction by Hz or CO. Mossbauer spectra showed clearly the disappearance of Fez+ with oxidation.

Amthauer et al. (3) report Mossbauer and UV spectroscopic studies on site distributions for Fe3+ and Ga3+ in garnets of composition Y3(Fe,Ca)601z. In particular, the disordering effect of thermal treatment on site distribution is emphasized. The magnetism of ( E U , S C ) ~ F ~ ~ O ~ ~ garnets has been studied by Stadnik (300) using both 57Fe and 151Eu Mossbauer effect. Measurements with an external field were used to obtain average canting angles. The magnetic properties are related to the cation site distribution. Annersten et al. (4) show Mossbauer results on synthetic nickel-iron olivines equili- brated at 1000 "C. The results indicate a strong preference of Fe2+ for M2 sites. Another type of mineral for which cation distributions are reported is graftonite (M,Fe)3(P0,)z. This structure has five-coordinate as well as six-coordinate metal sites. Nord and Ericsson (237) discuss Mossbauer evidence for five-coordinate site preference among M2+ ions. Shinno (294) presents a discussion of the observed asymmetry in the doublet spectra of oriented micas in relation to pleochroism

ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984 205 R

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and the sign of the field gradient. Minai and Tominaga (205) compare ferrous to ferric ratios obtained by Mossbauer spectroscopy to chemical data for 20 geological reference standards. Good agreement was obtained for most samples. Roy-Poulaon et al. (266) discuss their results from Mossbauer spectroscopy of a stony meteorite in context of the theories of condensation in the solar system. A wide variation in composition among the component chondrules was found.

Heller-Kallai and Rozenson (127) review the literature on Mossbauer spectroscopy of layer silicates with emphasis on criteria for identification of various minerals and on the re- lationship between Mossbauer parameters and structural features. Schwertmann et al. (283) studied the techniques to identify the poorly crystalline mineral ferrihydrite in soils and show the usefulness of combining Mossbauer results, X-ray diffraction, and chemical treatment.

A number of studies of sediments have appeared in the last 2 years. Johnston and Glasby (145) used both Mossbauer spectroscopy and X-ray diffraction to study variations in clay mineralogy among sediments from the Pacific basin near New Zealand. Suttill et al. (308) give Mossbauer results and other mineralogical data for core samples from tidal-flat sediments in East Anglia. Increased pyrite contribution to the 57Fe spectra with depth in the core was observed. Siebers et al. (296) used Mossbauer spectroscopy to study extraction of phosphates from wastewater sediments. Their results are complicated by the difficulty of distinguishing ferric phos- phates from hydroxides in the Mossbauer spectra but indicate the iron components are not removed as thoroughly as pre- viously supposed. Mannin and Jones (194) compare

the Great Lakes with phosphate measurements and conclude these sediments are saturated with phosphate. Manning et al. (195) report further Mossbauer studies on Great Lakes sediment, including measurements at 4 K which show the presence of ultrafine hydrated ferric oxide in thin layers -5 cm below the core surface. Fysh and Clark (96) report a Mossbauer study of the acid leaching of bauxites. Most of the iron is present as hematite before leaching. Aluminum- substituted goethite precipitates during HC1 treatment. Surprisingly, no akaganeite appears to be formed.

Coal is an environmental material continuing to receive the attention of Mossbauer spectroscopists. Most studies relate to the detection of pyrite, FeSz, and its transformations with various treatments. Pyrite is a low-spin Fe(I1) mineral with Mossbauer parameters similar to high-spin Fe(II1). It is often of interest to differentiate these two. VBrtes et al. (329) demonstrate that a combination of heat treatment at 900 "C and Mijssbauer spectroscopy can be used to differentiate pyrite from Fe3+ in biotite. The pyrite is converted to hematite with ita characteristic six-line spectrum. Gupta et al. (119) studied heat treatment of natural pyrites and report that both the appearance of intermediate sulfates and the temperature of conversion to hematite depend on crystallinity and the nature of impurities. The transformation to hematite was incomplete even at 800 "C for a coal sample. Bommannavar and Montan0 (33) report thermal decomposition studies on pyrite in coal undr inert atmosphere rather than in air. In these experiments pyrite converts to pyrrhotite, Fel,S. The presence of coal affects the rate of conversion and the spectral parameters of the pyrrhotite.

Evans et al. (85) give results on a large number of geological samples of pyrite and marcasite and on mixtures of the two. They show the ratio of the two minerals can be estimated from room temperature Mossbauer analysis, although the separate doublet components cannot be obtained individually. Mel- chior et al. (203) investigated the changes in iron mineralogy of oil shales during the retorting process, with and without addition of oxygen gas. Without oxygen the pyrite decomposes to pyrrhotite at relatively low temperature whereas carbonates are stable. With oxygen, hematite and magnetite are formed, although some pyrite remains even at 750 "C.

Guilianelli and Williamson (118) compare the effects on iron-sulfur compounds in coal by low-temperature ashing using the microwave and radio frequency method. Pyrite is not oxidized by either technique, but oxidation and dehy- dration occur for the iron sulfates. They report the recoilless fraction ratio for iron in sulfates to pyrite as 0.55. Jacobs et al. (142) do obtain significant conversion of pyrite to pyrrhotite by microwave heating, using higher frequencies and power

206R ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984

Mossbauer results on Fe2+/Fe P + ratios in sediment cores from

levels than above. They used magnetic separation following the treatment to concentrate the iron species for Mossbauer analysis. Jacobs et al. (141) also report a Mossbauer and magnetic study of coal gasification under various conditions. Pyrrhotite is formed at 700 "C in inert atmosphere, COz ga- sification produces magnetite, while in steam gasification reduced species such as wustite, Fel,O. and metallic iron are formed.

CATALYSTS A number of groups have used Mossbauer spectroscopy in

various aspects of catalysis research, continuing to make this one of the more popular applied fields of this technique. Le Caer et al. (174) give an extensive discussion of the charac- terization of iron carbides in Fischer-Tropsch synthesis. Literature results are reviewed and a new in situ kinetic study is reported for an Fe on A1203 and Fe(Cr) on A1203 at 523 K. The hyperfine fields are correlated with carbon content. On the basis of their results, a model is proposed for carburization of the catalysts. Lund and Dumesic (190) report further studies on silica-supported Fe304 catalysts. In this paper they examined the changes in Mossbauer spectra and catalytic activity with particle size of the magnetite. They emphasize evidence for the formation of a surface layer on the Fe304 in which Si4+ substitutes for Fe3+ in tetrahedral sites. Niem- antsverdriet et al. (230) studied in situ reduction processes on Fe-Rh/Si02 catalysts in the presence of H2 or CO, showing a marked increase in the iron reducibility by the presence of Rh. This catalyst appears to be useful in Fischer-Tropsch synthesis due to its direct production of ethanol.

Tricker et al. (315) used both transmission and conversion electron (CEMS) Mossbauer spectroscopy to study the am- monia synthesis catalyst Fe-Co/A120s. The reduced form of the catalyst contains an inhomogeneous bimetallic core sur- rounded by an oxide surface. Pattek-Janczyk and Hrynkiewicz (245, 246) report in situ studies on a commercial ammonia synthesis catalyst. The original oxides were reduced to metallic iron. Activation energies for both wustite and magnetite formation are reported which are higher than for pure phases and dependent on degree of conversion.

Kalashnikov et al. (149) studied the catalytic properties of iron-graphite lamellar compounds for high-pressure synthesis of diamond. Mossbauer spectroscopy provided important evidence on the stability of the complex and the absence of formation of metallic iron to any appreciable extent. Burriesci et al. (46) used X-ray, photoelectron, and Mossbauer tech- niques to study iron-antimony catalysts for ammoxidation. The changes produced by excess Sb are emphasized. Berry (24) reviews Mossbauer results for l19Sn and lZISb on tin- antimony catalysts, reports additional l19Sn data for calcined samples, and discusses the relevance of the various cationic species to the catalytic behavior.

SURFACE STUDIES Most Mossbauer surface studies use either emission from

a surface source or scattering techniques. At least one recent paper reports absorption experiments on a monolayer film: Shechter et al. (290) give a detailed description of their ex- periments with Sn(CHJ adsorbed on Grafoil. Measurements were taken parallel and' perpendicular to the surface. The two-dimensional system undergoes two transitions, a solid- state transition at -85 K and melting at -95 K. The 85 K transition is only observed for high surface coverage.

Leidheiser et al. (176) used emission from 57C0 to study the interfacial interaction between cobalt metal and poly- butadiene. Shinjo et al. (293) report Mossbauer and ESCA measurements on a very thin 57Fe layer vacuum deposited on %Fe substrate and then surface oxidized. Both Fe metal and an oxide similar to 7-Fe203 were clearly evident at 4 K, al- though at room temperature the oxide exhibited strong su- perparamagnetic relaxation. Meisel et al. (201) used CEMS and ESCA to study oxidation of steel in water containing chromate and chloride ions. The oxide layers were much thicker in the presence of chloride and gave superparmagnetic doublets in the room temperature and 80 K spectra.

Christensen and M0rup (57) calculate magnetic dipole fields for surface atoms in a-iron. Only the first layer is altered by the presence of the surface, but the shape anisotropy for microcrystals is affected.

MOSSBAUER SPECTROSCOPY

Okada et al. (241) report emission Mossbauer experiments using llgSb adsorbed on the surface of Fez03 and Cr203. Supertransferred hyperfine fields at the adsorbed ll9Sn were observed and related to the site geometry. No nonmagnetic surface layer was detected. Friedt et al. (91) studied the surface interaction between iron and antimony in multilayer films using 57Fe and lZ1Sb Mossbauer absorption. A large transferred hyperfine field is seen at Sb, much greater than for Sb diluted in a-iron. Tyson et al. (316) report Mossbauer studies of the magnetic properties of thin films of SBFe using probe layers of 57Fe. The surface magnetism has a different temperature dependence from the bulk, giving rise to large surface fields at low temperature.

In situ Mossbauer experiments on iron phthalocyanine adsorbed on a carbon electrode are reported by Scherson et al. (280). The quadrupole splitting decreased on immersion in electrolyte but no changes were observed with applied potential. Surface studies of a-Fe2O3 are reported by two groups. Yang et al. (338) used depth-selective CEMS to measure hyperfine fields as a function of distance from the surface. The measurement technique utilized a difference method to compare the fields from electrons of different en- ergies (and thus different depth). The bulk field value is reached at about 18 A, but a small decrease occurs at the surface according to these measurements. Shinjo et al. (292) preci itated a thin coating of 57Fe on a-Fez03 particles pre- paref from 56Fe. They also find a decreased field at the surface for room temperature measurements. The variation with temperature is similar to that for the y-FezO3 surface and corresponds to an exchange field about 60% of the bulk value. However the Morin transition occurs a t the same temperature for the surface layer as for bulk a-FezO3.

AMORPHOUS MATERIALS The sensitivity of Mossbauer spectroscopy to short-range

order makes it a popular technique for studying amorphous systems. Both glassy oxides and metallic glasses continue to be widely studied.

The metallic glasses prepared in thin ribbons from tran- sition metals with boron to stabilize the amorphous phase are ferromagnetic and of commercial importance. Determination of the magnetic properties is the main function of the Mossbauer measurements, but specific recent applications emphasize many different features. Arajs et al. (6) used Mossbauer spectroscopy to determine the various phases appearing during the crystallization process in FesrB16,Cx. The first step is precipitation of a-Fe, followed by formation either of Fe3B or Fe C. At high temperature these inter- metallic compounds decompose. Bhatnagar et al. (26) report the temperature dependence of the hyperfine fields in com- mercial Feai&izO. Crystallization occurs slightly above the Curie temperature of 695 K. Chien and Unruh (56) used sputtering techniques to produce amorphous Fel,B, samples with x = 0.1-0.7. The Curie temperature is highest for 70% Fe. A comparison is made between these samples and those prepared by liquid quenchin . However, the sputtering technique provides a much wi di er range of composition, and their results indicate discrepancies with some models of the magnetic field distributions. Dubois and Le Caer (81) report hyperfine distributions in liquid quenched Fel,B, with x = 0.12-0.25 and present a model of the structure based on relating the field distributions to the number of Fe-B neighbors.

Dunlap (82) measured the hyperfine field at the impurity site using a lZISb Mossbauer effect on Fe7gSbB20: The sys- tematics of the fields measured at nonmagnetic sites in fer- romagnetics are discussed. Greneche et al. (115) report texture effects in a metallic glass ribbon aligned by tensile strain. They used various angles for orienting the ribbon relative to the y beam. Gonser and Wagner (112) present a review of amorphous metals, emphasizing the results of Mossbauer studies. Gonser et al. (111) also report both absorption and emission (CEMS) Mossbauer studies on Fes3P5Cl12 which indicate surface oxidation and crystallization are responsible for changing the domain structure due to magnetoelastic effects. Lines and Eibschutz (180) interpret the Mossbauer spectrum of Fe76Bz4 in terms of correlation effects between hyperfine field, electric field gradient, and isomer shift. They show that line width analysis eliminates the need for specifyin the detailed form of the correlation. Kopcewicz et al. (1657

obtained Mossbauer spectra for several metallic glasses in the presence of radio frequency fields to determine the effect of the applied field on the crystallization process. A different type of amorphous metal, Mgl-,Fe,, was studied by Van der Kraan and Buschow (323), with emphasis on the magnetic properties. The systematics with Mg replaced by other nonmagnetic metals are discussed.

Muller-Warmuth and Eckert (219) give a comprehensive summary of both Mossbauer spectroscopy and nuclear mag- netic resonance applied to inorganic nonmetallic glasses. The J7Fe Mossbauer spectra of iron-tellurium oxide glasses are re orted by Bidczycka et al. (27). Boolchand et al. (36) used

dination sites for Te in As-Te glasses. The latter indicate a breakdown of the usual coordination rules of such s stems.

sorption results for the same system (310) as a function of arsenic concentration. Boolchand et al. (37) also discuss the relation between Mossbauer results and glass-forming tend- ency for the Ge-Se system.

Bonnenfant et al. (34) report a detailed study of the system Fe20 -BaO-B203 by 59Fe Mossbauer techniques. Lines ( 1 79) calcdates the spectra observed as a magnetic field is applied to a system with a distribution of electric field gradients and shows how this relates to the dominant sign of the field gra- dient. Schultes et al. (282) report Mossbauer studies of noncrystalline iron garnets prepared by sputtering. Litterst et al. (183) used 151Eu Mossbauer effect to study the magnetic properties of the spin glass Eul-,Gd,S.

Several Mossbauer studies have appeared recently on sil- icate glasses produced from gels. Guglielmi et al. ( 1 1 7 ) used alcoholic solutions of Si(OC2H5), and Fe(OC2H5)3 as starting material adding water to form the gel and then neat treating. The Fe2'/Fe3+ ratio is strongly dependent on the iron content of the glass and on the temperature. Uetake and Kikuchi (317) report Mossbauer studies of the gel formed between Fe3+ and water glass. These authors conclude that Fe3' reacts with the silicate during gel formation.

For a quite different sort of amorphous material, Albanese et al. (2) report Rayleigh scattering experiments of Mossbauer radiation from a silicon rubber. These experiments deal with the atomic motions giving rise to transition between rubber, glass, and crystalline state. Litterst (181) reviews use of the Mossbauer effect to study structural rearrangements in non- metallic amorphous materials.

The low-temperature behavior of water absorbed in the cation-exchange Nafion membranes was studied by using a number of techniques by Boyle et al. (41). They observed the disappearance of the 151Eu Mossbauer effect for Eu3+ Nafion at about 220 K, indicating an unusual glassy form for the absorbed water. Gao and Rees (102) report Mossbauer studies on absorption of water and alcohols by iron-containing zeolites.

Nagy et al. (223) used applied magnetic fields to study the ligand field distribution in frozen aqueous solutions of Fe- (C104)2. Mossbauer studies of frozen alkylbenzene solutions of tris(acetylacetonato)iron(III) are reported by Sakai et al. (269) and related to the hot atom chemistry of the corre- sponding 6oCo compound. Katada et al. (154) used the l19Sn Mossbauer effect to determine the configuration of Sn(1V) in frozen aqueous solutions of mixed hydrogen halides. Burger et al. (4) report a study using llgSn and 07Fe of liquid samples trapped in the capillaries of porous silicate glass (so-called "thirsty" glass). Mossbauer spectra were obtained for solutes in liquid solution which at least in some cases seem to reflect the properties of the solution rather than any interaction with the glass surface.

Diamant et al. (77) used 57Fe Mossbauer effect to charac- terize the adsorbed iron in the interlayers of montmorillonites. The temperature dependence of the Mossbauer fraction for adsorbed Fez+ exhibited a marked decrease at about 210 K, interpreted as due to melting of the interlayer water. The adsorbed Fe3' did not show this effect.

INTERCALATION COMPOUNDS Herber (128) reviews Mossbauer work on these materials

formed by imbedding guest molecules in the interlayers of low-dimensional solids, emphasizing the results from his laboratory. Katada et al. (155) report Mossbauer results on iron and tin intercalated in NbS2. Isomer shifts of both 57Fe and l19Sn correspond to valence state 11, while lattice tem-

ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984 * 207R

l2 B I emission spectroscopy to distinguish 2- and 3-fold coor-

The same group reports both 1291 emission and l2 K Te ab-

MOSSBAUER SPECTROSCOPY

peratures indicate polymeric bonding to sulfur. Rouxel and Palvadeau (265) used Mossbauer spectroscopy to study the picoline and ferrocene in FeOCl intercalates. Some Fez+ is seen in the FeOCl resonance at high temperature and electron hopping occurs even higher. The ferrocene is ionized to ferricinium, which apparently participates in the electron exchange. Millman et al. (204) report analysis of low-tem- perature Mossbauer data on FeCl intercalated in graphite. Evidence for a three-dimensionaf magnetic interaction is presented. About 20% of the iron sites are converted to Fe2+ at low temperature. Vaishnava and Montano (320) studied reduction and Fischer-Tropsch reactions on FeC13 intercalated in graphite by using in situ Miiesbauer measurements. Flowing H2 at 400 "C converts the FeC13 to FeC1, and partly to a-Fe. It appears that some of these latter are present on the surface as well as intercalated between layers.

SEMICONDUCTORS Although a discussion of papers on semiconductors has been

included in previous editions of this review, work in this field appears particularly active in the last few years. These studies usually involve a Mossbauer probe atom in a different sem- iconductor material.

Concerning group 4 semiconductors, Nielsen (229) treats substitutional Sn by a theoretical model based on the adiabatic bond-charge description of the lattice vibrations. Estimates are made for changes in force constants at the substituted site. Van Rossum et al. (325) use cluster calculations of the ex- tended Huckel method with charge consistency to analyze the quadrupole interactions for l25Te and lBI implanted in silicon and germanium. Nanver et al. (225) report emission exper- iments for ion-implanted llsmSn in amorphous group 4 sem- iconductors. Although the amorphous materials have similar Debye temperatures to those for crystalline phases, charac- teristic differences are observed in the line shape and position. Kemerink et al. report extensive studies of laser-annealed tellurium implanted silicon. Three radioactive sources were used: llemTe, lZSmTe (158), and lZsmTe (159). Several distinct charge states are observed for the latter two sources, depending on the amount of doping.

In a study of GaAs, Williamson and Gibart (336) prepared Te-doped single crystals by liquid phase epitaxy. Unlike most studies of this type, the doping was with nonradioactive 12Te for absorption experiments. Donor and acceptor sites were very similar according to the Mossbauer ex eriments and consistent with cubic spmetry. Antoncik and)Gu (5) discuss the interpretation of "%n isomer shifts in group 3-5 semi- conductors in terms of band theory. Their calculations show a distinct difference between the nature of the impurity charge state for tin as donor or acceptor, the latter being described by a neutral tin in a cluster. Weyer et al. (334) report ex- perimental studies of substitutional tin in group 3-5 com- pounds. Their results indicate the observed tin charge state relates to the ionicity of the host compound.

Langouche et al. (173) studied lzsTe implanted in single- crystal tellurium at liquid-nitrogen temperature. They find evidence for amorphous regions around the im lanted nuclei. Seregin and Nasredinov (286) used lWAu to stufy the impurity site in amorphous AszSea and relate these results to the lack of electrical conductivity observed. Both 67Fe and ll9Sn Mossbauer effect studies are reported by Nasredinov and Ermolaev (226) on the charge states of impurities in the oxide semiconductor COO.

MISCELLANEOUS APPLICATIONS This particular section of the review has been expanding

in the last three of this series. In 1980 there were five ref- erences; 1982 has 19 references; this year there are over 50 references. This has resulted from vigorous exploration by investigators for new areas of application by Mossbauer spectroscopy. Medical applications include the measurement of ferritin concentration in normal and abnormal erythrocytes from patients with P-thelassaemia, sickle cell disease, and sideroblastic anemia (140). Another study is that of tissue cultures of murine erythroleukemia cells (240). Two tin studies are the examination of possible antitumor organotin compounds (17) and some tin glauconates important for ra- diopharmaceuticals (306).

Mossbauer s ectroscopy continues to be an invaluable ex- perimental tec K nique used to study pottery of ancient civi-

208 R ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984

lizations. Often the data obtained can be used to interpret the firing conditions under which the pottery was produced, and in other instances, something about the original clay used. Gancedo et al. (98) studied 19 South Italic Greek-type ce- ramics. Sat0 et al. (274) examined ancient Japanese ear- thenware, Wagner et al. (332) studied ancient ceramics from the region of Berlin, and Calogero and Lazzarini (50) inves- tigated Byzantine and Venetian graffito ceramics. In studying 13 different clays, Maniatis (193) fired them to different temperatures to determine the effect of the calcium content on the iron oxide transformations in these various clays as they are fired. Another interesting paper is that of Longworth et al. (189) in which they discuss their study of an excavated, medieval stain glass samples to understand the color action of iron and its relationship to glass making conditions. Mossbauer spectroscopy has been used in the past to assist in the characterization of airborne particles containing iron. More recently, Matoba et al. (198) compared the Mossbauer results of fine particulates and coarse particulates.

Mossbauer spectroscopy is a very effective technique for studying electrodeposits on electrodes. Ioffe et al. (135) studied nickel deposited onto a cathode using a 1 % impurity of 67Fe. They were able to study the nickel cathode before and after degassing. VBrtes et al. (330) also studied electro- deposited nickel with 6 7 C ~ introduced as an impurity. In- formation was obtained on the magnetic orientation of several different electrodes. Blomquist et al. (31,32) studied poly- meric iron with phthalocyanine oxygen electrodes. The electrocatalytic activity was investigated as a function of various methods for the preparation of these electrodes. llgSn Mossbauer spectroscopy was used to study heat treatments after electrodeposition of tin onto iron foil substrate by VBrtes et al. (331). Other electrodeposition studies are reported elsewhere in this review (280, 309).

The effect of laser annealing can be easily studied with Mossbauer spectroscopy. After Dekhtyar et al. (74) examined nonequilibrium point defects which were generated in a Nb-Fe system due to the action of a shock wave produced by a pulse laser, they could identify the intermetallic compounds. In another study Damgaard et al. (66) introduced Sn and Fe as impurity atoms into Si and GaAs single crystals by first ir- radiating a thin metallic surface layer on the crystals and then annealing them with light pulses from a Nd-glass laser. In other studies laser annealing has been used following the ion implantation of a specific atom impurity into another sub- stance. These studies include Fe in Si (172), Te in GaAs, GaSb, Gap, and InP (324), and Sb, Te, and I in Ge and Si (67, 72,68). There have been many papers published which involve ion implantation during the last 2 years. Only a few of these are mentioned in this review. Papers by Shinno and Maeda (295) and Sawicki et al. (277) indicate that after being implanted into diamond, iron experiences a high internal pressure. The effect of nitrogen's being implanted into both medium and high carbon steels is reported in two different papers (89,258). Schreyer et al. (281) describe the formation of an iron hydride which they have identified as e-Fe&.,. This particular phase which has been produced under extremely high pressures of hydrogen is obtained by implanting ions into a-iron films at liquid nitrogen temperatures. l19Sb was im- planted in platinum and studied by usin Sn Mossbauer

tungsten was studied by using ls1Ta Mossbauer spectroscopy. Another technique for obtaining single atoms or molecules

in a solid lattice is through matrix isolation. After the Mossbauer element or molecule in a gas state has been mixed with a gas substrate, the two species are allowed to condense on a cold surface. By use of this technique DzTe and H2Te have been isolated in argon. Montano et al. (212) note a 10% increase in the quadrupole splittin for the D2Te and explain

the D-Te bond. In another paper Bag io Saitovich et al. (11) report their study of the isolation of mFe in solid ammonia and also in ammonia/xenon mixtures. They identify primarily one chemical species that is formed, FeNH3.

There are numerous papers reportin studies on the effect

few are mentioned here. Hayashi and Takahashi (125) discuss the effect of helium ion irradiation on the amorphous alloy FeaNia1,B6. They note that surface blistering was observed after irradiation. They used CEMS to examine the surface.

spectroscopy (231). Implantation of hy d rogen ions into

it as the result of the [1/r3] cause 8 by a slight contraction of

of irradiation on a variety of different f inds of materials. A

MOSSBAUER SPECTROSCOPY

Nishida et al. (233) used neutron irradiated potassium boro- silicate glasses and noted decreases in the isomer shift and increases in the quadrupole splitting after the irradiation, which they attribute to a decreased asymmetry around the iron nucleus produced by elastic collisions of the charged particles with many of the atoms in the glass. Other materials studied are the amorphous alloy F e d z o (IN), iron and garnet films (121), 304 stainless steel (126), bcc metals (196), and niobium (339).

There have been numerous papers on zeolites (101,100,87, 321), thin fiis (83,132,80,20), and slage used in steel making (40,259,108). Goodman and DeKock (113) examined spec- imens of duckweed, soybean, and peas which had been iso- topically enriched in 67Fe by growing them in nutrient solu- tions which contain 57Fe. All these substances show the presence of iron in the ferric form.

In a paper on one of the more interesting recent applications of the Mossbauer effect Mkrtchyan et al. (207) describe a method for measuring the speed of sound in condensed media by the modulating characteristics of the Mossbauer spectra and using ultrasonic oscillations. With this technique, the speed of sound can be measured with an accuracy of 0.3%.

ACKNOWLEDGMENT We have been assisted in the preparation of this review by

Vir ia E. Stevens, who extensively proofread the manuscript, anEanet Gibson, Mary Jane Winfrey, and Joyce Witherspoon who assisted with the typing. We also wish to note our ap- preciation to Richard White and Janet Gibson, who aided in the retrieval and organization of the literature. Finally we acknowledge the support of the National Science Foundation to J. G. Stevens (Grant No. TFI-80-20773) and to L. H. Bowen (Grant No. EAR-82-18739).

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Nuclear Magnetic Resonance Spectrometry

John R. Wasson'

SYNTHECO, Inc., 1920 Industrial Pike Road, Gastonia, North Carolina 28052

This review covers the published literature from July 1981 to July 1983 although some citations of other work are also included. As noted in earlier reviews (1) the volume of lit- erature published in a 2 year period is impossible to summarize in such a short space. Instead, it is hoped that this effort serves as a guide to the recent books, reviews, and develop- ments of use to the reader.

With the general affordability of computers there is coming an onslaught of software, instructional tools, and other ap- plications. Educational software on lH NMR spectroscopy (2) and a new Wiley Heyden journal Computer Enhanced Spectroscopy have already graced the scene as have an in- creasing number of papers dealing with computer software and hardware and NMR spectrometry.

BOOKS AND REVIEWS The books (3-46) on NMR spectrometry cover fundamen-

tals to state-of-the-art developments with a significant number

l F o r biographical material, see the review o n electron sp in reso- nance.

of them dealing with biological applications. Table I lists review articles. For convenience, the references in Table I are collected separately in the bibliography. The reviews by Kuchel(47) and Levy and Craik (48) deserve special mention since the former deals with handling biological samples and the latter gives a good overview of current developments.

APPARATUS AND TECHNIQUES A method involving surrounding the particles of the powder

with a liquid of the same magnetic susceptibility as the powder has been presented to reduce the severe magnetic suscepti- bility broadening of NMR spectra of powders (49). High- resolution lH NMR in solids can be obtained by isotopic dilution of protons in a deuterated solid combined with ma ic-angle spinnin (50). Methods for measuring the energy an% temperature ofthe secular dipole-dipole interaction of nuclear spin systems in high field have been described (51). Magic-angle sample spinning has been combined with two- dimensional NMR methods to obtain high-resolution chemical shift dipolar spectra (52). Variable-angle sample spinning high-resolution NMR of solids (53) and an alternatlng pulsed

212 R 0003-2700/84/0356-212R$01.50/0 0 1984 American Chemical Society