Anal. Chem 1980, 52, 175R-185R

Mossbauer Spectroscopy

John G. Stevens”

Department of Chemistry, University of North Carolina at Asheville, Asheville, North Carolina 288 14

Lawrence H. Bowen

Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27607

INTRODUCTION This review is the eighth in an on-going series on Mossbauer

spectroscopy being published biannually by ANALYTICAL CHEMISTRY. This current one covers the literature surveyed since the last review (297), so articles from the latter part of 1977 to the end of 1979 have been considered. Almost 3000 different scientific articles on the Mossbauer effect were ex- amined as we attempted to select less than 15% of them for inclusion in this review. The applications of Mossbauer spectroscopy have continued to be developed during the past two years; especially rapid growth has been seen in industry. Unfortunately, however, much of this work does not get published. Also the number of countries in which Mossbauer spectroscopic research is being planned or begun continues to increase. A few newcomers include Cuba, Peru, Turkey, Thailand, and Saudi Arabia. A significant number of papers are now also coming from China, as the rebirth of the basic sciences takes place there.

The observations of several new Mossbauer transitions have been reported in the literature since the last review. These include the 42.9 keV transition in 240Pu (158), the 78.7 keV transition in li3Yb (52), and 10.1 keV transition in 13’La (112). While most of the transitions in the past five years have been of little interest because they require low temperatures and have extremely small intensities, the most recent ones reported show more promise. 240Pu allows for studies of an element not before possible.

The vast majority of the papers continues to deal with investigations using 57Fe, far and away the most popular isotope, and its runner-up, l19Sn. A number of other isotopes are becoming more established as the information gleaned from studies on them using Mossbauer spectroscopy is now more easily understood. These isotopes include IgSAu, ‘j1Eu lZ9I, ‘“Sb, and 125Te. Combined they provided topic for -206 articles during the reportin period of the review. Articles

appearing far less frequently. A major book entitled “Mossbauer Spectroscopy and

Transition Metal Chemistry” (133) has recently been pub- lished. The authors, Gutlich, Link, and Trautwein, have done an excellent job covering the material indicated in its title. “Mossbauer Isomer Shifts“, edited by G. K. Shenoy and F. E. Wagner, is a major contribution to Mossbauer spectroscopy, containing almost 1000 pages of contributions from -25 leading scientists (283).

The proceedings of two international Mossbauer conferences held during these past two years have been published. The first, held in Kyoto, Japan, during the summer of 1978, had over 250 papers presented (320). In September of 1979, an- other conference was held in Portorui, Yugoslavia, the pro- ceedings of which should be available by the time this review goes to press. The second and final volume of the international conference held in Romania in 1977 was also published during the period covered by this review (22). One other major conference published was “Workshop on New Directions in Mossbauer Spectroscopy”, held at Argonne National Labo- ratory during 1977 (251). As well as these larger international conferences, there has been a marked increase in national or regional meetings.

The Mossbauer Effect Data Center, having replaced the annual “Mossbauer Effect Data Index” with a monthly in- formation journal, the Mossbauer Effect Reference and Data Journal, is now totally self-supporting as it supplies the

in which 161Dy, 237Np, 170Yb, %+ Ru, ‘j5Gd, and lslTa are topics

0003-2700/80/0352-175R$O 1 .OO/O

Mossbauer community with its bibliographic and data needs. The first two volumes of the Journal have been successful and well received. We have used the facilities of the Data Center extensively in the preparation of this review.

Because of the great variety of applications, there are a large number of reviews published. These applications-oriented reviews using Mossbauer spectroscopy center on topics such as hydrogen systems (335), polymers (192), ferric oxides and hydroxides (41), catalysts (33), corrosion (285), organoiron (240), surfaces (155), and coatings (34). Numerous Mossbauer biological reviews have appeared in the literature including ones on hemes and hemoproteins (201,202,226), peptides and proteins ( 8 1 ) , and iron porphyrins (273). Two good general reviews on metallurgy have appeared (100, 153) as well as reviews on radiation defects (281), amorphous magnetic rare earth alloys (48), backscattering applications in metallurgy (259), and impurity host force constant changes (123). The aspects of mineralogy which have been reviewed are silicate minerals (18) and thermal and radiation effects on minerals (68). Topics dealing with Mossbauer methodology include source materials (296), double resonance (212), high magnetic fields (49), and spin crossover (129). The 1976 literature has been extensively reviewed by Donaldson and Tricker (86).

The most difficult task is always that of selecting only a small percentage from all references available for inclusion in this review. I t is never an easy task to limit the number of papers on which we wish to report. I t is unavoidable that this review is heavily weighted towards those areas in which we ourselves are interested. As in previous years the very active research in biological materials and magnetic hyperfine studies has not been included because we felt too limited in our understanding of these areas to give adequate coverage.

INSTRUMENTATION AND EXPERIMENTAL TECHNIQUES

Improvements in precision and reliability have accounted for most recent developments in spectrometers. Dunham describes a spectrometer (88) which is designed specifically to maximize available information. I t has the capability of varying both the sample temperature (2-350 K) and the ap- plied magnetic field (M T). Genand-Riondet and others (110) have developed an improved electromagnetic velocity drive by suppressing the fundamental resonance frequency in the moving rod. A constant velocity spectrometer which is free of long-term instrumental and radioactive decay drifts in the count rate is described by Sarma et al. (274) . Taragin gives description of an inexpensive digital triangle wave generator which can be used in a Mossbauer spectrometer without any internal connections to the multichannel analyzer (304).

An alternative approach to the conventional Doppler- scanning method is suggested by Baldwin (16). He shows that the ?-ray frequency spectrum can be determined by obser- vation of the time distribution of delayed coincidence counts of 7’s that are transmitted by a stationary resonant filter. He also discusses several possible experiments. In another paper discussing spectrometer improvements, Delyagin (76) describes a double Mossbauer spectrometer for measuring small line shifts.

Minicomputers and microprocessors are becoming ever more useful, mainly as they expand the capabilities of the spectrometer. Although some of these are used simply as data acquisition systems, e.g., PDP-4 (336) or PDP-9 (with a CA- MAC system for interfacing) (2531, others are inexpensive and

175 R C 1980 American Chemical Society

flexible enough to offer potential for future applications and developments (318,254, 319). One system functions as a data processor (120), a development which will undoubtedly grow both in use and sophistication. Microprocessors will provide more and more unique services for spectrometers in the future. One present example is the use of a microprocessor to separate the elastic scattered intensity from the inelastic one in the vicinity of Bragg reflections in a Mossbauer diffractometer (271).

Kobeissi and Hohenemser (169) describe a high precision Mossbauer furnace capable of reaching temperatures up to 1100 K with a long-term stability of 0.02 K and inhomogeneity of better than 0.05 K.

Chappert’s group in Grenoble has developed a high field system using Bitter magnets (305). A maximum field of 16 T is obtained with a current of 15000 A.

The glass cryostat described by Pasternak and Shamai (244) avoids the difficulty of sealing mylar windows to a ground open-end glass surface by using a special lower metal section that is sealed to the glass. Other Dewars that have been described are those for varying the temperature (54), using a magnet system (36), and changing high pressures (193). Lowering the temperature down to 20 K in a conversion electron Mossbauer spectrometer has been reported by Sawicki e t al. (277).

A relatively inexpensive high counting system is described by Viegers and Trooster (329). By using the integrating counting technique, they are able to obtain high quality lg7Au Mossbauer spectra. Pawlowski and Cudny (246) have designed a multiwire proportional counter which is excellent for >’Fe studies because it has count rates up to 1.5 x lo6 cps with a gas amplication of 100 in the energy range of 3-15 keV. An improvement for proportional counters is accomplished by a rise time discriminator (164).

Jaggi and Rao (151) have developed a combination detec- tor-spectrometer system which can be used for the quanti- tative measurement of the ratio of ferrite to austenite in stainless steels. The procedure is rapid, nondestructive, inexpensive, and reproducible.

Improvements in conversion electron Mossbauer spec- troscopy are demonstrated by Carbucicchio (44). He uses a @-ray spectrometer to differentiate the electron energies and can, therefore, study materials a t different depths. The ad- vantages of this particular apparatus are that studies can be made in the temperature range of 74-800 K and the sample can be rotated. Massenet (210) has extended the temDerature down to 4.2 K.

Liljequist, Ekdahl, and Baverstam (187) have computed for the total transmission as well as the transmission into various angular and energy intervals of electrons from different depths in conversion electron Mossbauer spectroscopy (CEMS) of 57Fe absorbers. In a later work they discuss the interpretation and some practical analysis techniques for depth selection using CEMS (186).

Mbllen and Stevenson (225) describe a conversion electron detector using microfoil in which they are able to obtain a high signal-to-noise ratio and high efficiency. Owens, Chien, and Walker have investigated depth profiling of the magnetic hyperfine field with ultrathin films of iron (238).

The analysis of depth-selective Mossbauer effect data is described by the group at the University of Sofia (40,124,125). An empirical method of quantitative analysis is given.

Other topics related to instrumentation which have been described in the literature include a low-temperature me- chanical press for high pressure experiments (3381, a special cell for studying catalysts and small particles in the tem- perature range of 78-725 K (55) , and an apparatus for in- vestigating single crystal surfaces by Mossbauer effect emission (11).

Several laboratories are involved with proposing or ex- perimenting with the use of synchrotron radiation as a source for Mossbauer spectroscopy. The group a t the Kurchatov Atomic Energy Institute in Moscow has roposed the following

(13): After a preliminary monochromatization of the syn- chrotron radiation using Ge monocrystals, the coherent background is suppressed by using a purely nuclear reflection followed by a reduction of the noncoherent background using an analyzing crystal. Some preliminary experimental results have been obtained. They also discuss the time dependence

176R ANALYTICAL CHEMISTRY, VOL. 52, NO 5, APRIL 1980

experimental procedure for observing 7p Fe resonant transition

of delayed radiation which undergoes resonance Bragg scat- tering (157).

In another paper Cohen, Miller, and West (57) report to be the first to observe nuclear excitation using synchrotron radiation A very small resonance effect was observed by scanning their X-ray monochromator over the nuclear exci- tation energy. From theory Trammel1 and Hannon (311) discuss the quantum beats that will be produced when highly collimated pulses scatter on very small enriched single crystals a t the Bragg angle.

Mossbauer spectroscopy continues to be a widely used technique for investigating implantation. Recently, using 57Fe, these included studies on implantations into Si, Ge (177, 1781, Cu-Fe alloys (152, 197), Ag-Fe alloys (198), and A1 (276). A number of other isotopes have also been used. Xe has been implanted into diamond (323), Mo, W, T a (264), and Fe (263). An on-line Mossbauer system studying for 83Kr into A1 at low temperatures is described by Gutlich and others (131). Cs has been implanted into diamond (324) and iron (245). Others include Te and D into iron and nickel (79, 342), I’IEu into

Mossbauer spectroscopy studies of matrix isolated species provide data which can be used with good available models to obtain nuclear parameters and/or electronic state infor- mation. Dyson and Montano (91) have studied isolated FeMn molecules. The type of molecules formed was identified along with their electronic ground states. In another study monomer and dimer halide molecules of iron, tin, and europium were formed and investigated (190,191). Montano and others (221) have measured the effective internal magnetic field at the jSFe nucleus in monovalent iron in its 6D state. Specifically they were able to uniquely determine the ground-state Krammer’s doublet. While the usual matrix for isolation is one of the rare gases, Pasternak and Barrett (243) have used the matrix isolation method to study the phase transition in methane. They warn that one must be careful, however, that chemical reactions do not take place between the Mossbauer isotope and the matrix where rare gases are not used (23).

Other additional information can be obtained by using single crystals. For example, Gibb (113) discusses procedures for determining the orientation of the electric field gradient (EFG) tensor. Only the sign of the EFG is sought in more simple situations (108); other situations are more complicated because both the magnetic and EFG axes are sought (127). Often magnetic fields are applied to the single crystal to assist in the determination of the magnetic structure (2, 160). Spiering (293) describes a systematic procedure for evaluating the EFG from single crystal measures and large magnetic fields. M$rup and others (223) have observed the effect of external fields up to 85 kCr on spin-spin relaxation in a single crystal. In another case the behavior of domain structure during magnetization of thin single crystals has been studied (94). Polarization effects have been reported in single crystals of FeC!2-4H20 (294). While most of the work has been done using 5‘Fe, Ernst et al. (97) have determined the EFG’s of Os in metals of Os and Re using the 137 keV resonance transition in lE60s.

Scattering experiments in which the scatter does not contaln Mossbauer atoms are possible and they provide useful data. For example, Soltwisch et al. (291) have determined. the structure factor for glycerol. They also have obtained in- formation on molecular motion of glycerol as a function of temperature (95). Other substances studied have been polyethylene (307), copper and aluminum (2081, and alkali halides (209). Kovalenko et al. (172) report observing ex- perimentally, for the first time, a connection between the polarization characteristics of coherent Mossbauer scattering and the magnetic structure of the crystal.

One of the simple ways of studying phase transitions of any sort is by using a constant velocity spectrometer set on an appropriate absorption peak. When the temperature is varied and the counts are plotted vs. temperature, a phase transition will cause an abrupt change in the plot. Chien et al. (61) have used this method to determine the magnetic ordering tem- peratures of several amorphous iron-boron samples. Gupta et al. (128) have used the technique effectively to observe the magnetic transition in Fe2Mo04.

Descriptions of a number of miscellaneous experimental set-ups have appeared in the literature during the last two years. One of these is a proposal and demonstration of a

iron (231), and B Sn into Te and fcc metals (236, 266).

John G. Stevens is a professor of chemistry at the University of North Carolina at Ashe- ville He received his €3 S (1964) degree in chemistry and Ph D (1969) in physical chem- istry from North Carolina State University. He has soent three summers at Aroonne National Laboratory, a leave of absgnce at Max- Planck-Institut fur Festkorperforschung and a year-leave of absence in addition to two summers at the University of Nijmegen His main research interest is Mossbauer spec- troscopy and its applications to the study of antimony compounds and minerals His ad- ditional interests are with the problems of evaluation and dissemination of scientific data and information He is the head of the Mossbauer Effect Data Center from where he co-edits the Mossbauer Effect Reference and Data Journal He is on the executive board of the International Commission for Applications of the Mossbauer Effect (ICAME) He is a member of the American Chemical Society American Physical Society Sigma Xi Sigma Pi Sigma and the Chemical Society

Lawrence H. Bowen received his 6 S from Virginia Military Institute in 1956 and the Ph D in physical chemistry from the Massachusetts Institute of Technology in 1961 He has been at North Carolina State University since Sep- tember of 1961 and is now professor of chemistry His research interests include ra- diochemical techniques in analytical chemistry and applications of Mossbauer spectroscopy, in particular to inorganic and organometallic compounds of antimony and to iron oxides in soil He is a member of the American Chem- ical Society, American Physical Society, and Sigma Xi

method for cbtaining Mossbauer spectra when the source and the absorber are a great distance from each other. That is, Pound and Vetterling (255) have used guides for ?-rays which nearly completely reflect -,-rays when the grazing is quite small. Other experiments have included a Mossbauer po- larimeter (1381, ultrasonic excitation (219, 220). and an ul- trafast shutter for resonant ?-rays (12). In another experi- ment, called "quantum beats of recoil-free radiation", Perlow (252) frequency modulates a source of 5 i C ~ by vibrating it with a piezoelectric crystal so that one of the lines of the resulting multiple emission spectrum is absorbed. The spectrum re- maining is time dependent and its harmonic composition and relative phases are sensitive to small energy shifts.

SPECTRAL ANALYSIS In two recent papers (70, 71) Dattagupta develops the

stochastic theories of line shape for interpreting data from time-dependent hyperfine interactions. In particular. he treats the case in which the frequency of the radiating system is comparable to the rate of fluctation in the surrounding bath. The theory developed is much more general than previous ones. The solutions are given in terms of a transition matrix which contains information about the random properties of the Hamiltonian.

In another area of relaxation, Belozerskii (28, 29) has con- tinued his experimental and theoretical studies of micro- crystals and superparamagnetism. In these current papers he considers the effects of the particle size distribution on the spectra. Also considered are two determinations, Le., the anisotropy energy and the diffusion coefficient of the vector of magnetization.

The effect of diffusion on the Mossbauer line shape is calculated analvticallv bv Bender and Schroeder (32). Thev have considered the particular case of diffusion via vacancies. In another paper Kucera and Kucera (173) evaluate previous Mossbauer line diffusion broadening by an exponential fi t .

As Mossbauer spectroscopy continues to mature, the wide variety of phenomena that affect the line shape are being more clearly understood. For example, Pearson and Williams (247) have considered the result when a quadrupole-split powdered absorber is situated in a larger external magnetic field. Spiering and Witzgall (295) recently considered sodium ni-

troprusside. They have studied the effect of absorber thick- ness and polarization of the absorber. Other investigations on line shapes include the effect of an external periodic perturbation of ultrasonic frequency on a source (316), the effect of the dispersion parameter in high precision data of 237Np Mossbauer spectroscopy (14), and the effect of inelastic scattering of the order-parameter fluctuation near phase transitions (346).

In recent years there has been an increased interest in texture, an observable phenomenon of Mossbauer spectros- copy which results from preferred orientation of microcrystals. Nagy (228) considers texture caused by deformation and also suggests a method for preparing texture-free absorbers.

All too often in Mossbauer spectroscopy errors are un- derestimated because individuals use computer calculated errors, the programs for which w e a least-squares method with weighting factors that are inversely proportional to the dis- persions of the value being measured. Gavrilov and Zemskov (109) consider this problem and suggest an alternate treatment of the data which considers the velocity errors due to non- linearity. velocity noise, etc.

Two papers on computer fitting of Mossbauer data are worthy of mention here. Lagunov and Polozenko ( I 75) de- scribe an algorithm and program written in .ALGOL-60 which is very flexible allowing for a sum of Lorentzian or Gaussian lines. A more sophisticated program is reported by Rue- benbauer and Birchall (268) which has very general applica- bility. Its main features include the use of transmission in- tegral procedures, a full Hamiltonian diagonalization for ar- bitrary spins, a magnetic field distribution analysis to the first order, a single or polycrystalline intensity calculation for arbitrary transitions, and the options for including Goldan- skii-Karygin or texture effects.

THEORY One of the major concerns of recent theoretical papers has

been what to expect for line shapes when the -/-ray is polarized. Most of these are scattering type geometries. Banerjee (20) investigates the theoretical results when there is relaxation and polarization. He proposes that such cases will result in additional Mossbauer lines, the analysis of which can be useful in obtaining information on the dynamical processes in an atomic system. The discussion of this newer paper builds on an earlier paper in which Banerjee and Blume (21) consider polarization analysis of emission lines in the presence of re- laxation. Daniels (67) considers the more specific problem of determining the spin arrangements in magnetic materials by using polarized y-rays. Another specific applications area is that of conversion electron Mossbauer spectroscopy in which the y's are polarized (242) .

Hartmann-Boutron (137) continues her work on the use of Liouville relaxation supermatrix R derived by the method of the equation of motion of the density matrix and the super- matrix R' obtained by the resolvent method. The range in which both of these are valid is explored and an analytical expression is derived for the particular case of I7'Yb. Spin- spin relaxation and its effect on the Mossbauer spectral line shape is further investigated by Afanas'ev and Onishchenko ( 5 ) . They have obtained a single function for systems of cubic symmetry and 2-0 nuclear transitions in which it is possible to obtain the frequency dependence of the relaxatior? func- tions.

More attention continues to be placed on the understanding of Mossbauer scattered radiation. Several developments have been discussed at the beginning of this section, but two others are also noteworthy. Meisel and Keszthelyi (213) have de- termined relations for the hyperfine fields from perturbed angular distributions of the scattered Mossbauer radiation. As an application they discovered that the quadrupole in- teractions are the main causes for the line broadening in stainless steels. In the other study Bashkirov and his group (24, 25) investigated y-ray scattering in which double reso- nance was considered. The double resonance is the combi- nation of Mossbauer resonance with the nuclear magnetic or quadrupole resonance. Particular problems arise when the frequency of the rf field is equal to the Larmor frequency of the nuclear spin in the excited state.

Several papers consider the effects of lattice anharmonicity. Goldstein and Peierls (115) have developed a model for low temperature. Matsushita and Matsubara (21 I ) consider

ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980 177R

metallic fine particles. Roy et al. (267) investigated the ex- pected effect of anharmonicity of the second-order Doppler shift.

Other theoretical developments discuss the determination of the interference effect in the Mossbauer spectra by E2 transitions (250), the result of the acoustic modulation of y radiation (270), the effect of inhomogeneous ultrasonic modulation of y radiation (218), the effect of magnetic Brownian particles on the line shape (92) , and the develop- ment of a method to determine the sign of the hyperfine interaction through combination of the Mossbauer effect and time-dependent perturbed angular correlations techniques (3).

LATTICE DYNAMICS The temperature dependence of the various Mossbauer

parameters may be related to the dynamic properties of the solid state lattice. These include primarily isomer shift and recoil-free fraction, f, variations. de Grave et al. (74) studied these in two compounds of the spinel series Fez(]- ,Mgl+,Ti O4 having Fe3+ in both octahedral and tetrahedra( sites. TAey found the Debye temperatures for the two sites were identical within experimental error, but differed for the two compounds with y = 0.8 and 0.9. Kobeissi et al. (168) used both source and absorber experiments to search for isomer shift anomalies around the Curie point of iron. In contrast to some earlier work, no magnetization effects were observed in the isomer shift.

Friedt et al. (106) studied the 237Np Mossbauer effect in ternary oxides of Np(VI1). In addition to isomer shift and quadrupole coupling data, they obtained the detailed tem- perature variation of peak area for CsNpO, and fit this to a Debye model. Friedt et al. (104) also studied 237Np emission spectra following a decay of 241Am in a variety of matrices. A single resonance was observed in the metallic hosts, whereas several different valence states occurred systematically in oxide hosts. The temperature dependence off in Am metal obeyed the Debye model. Sitek et al. (287) determined the Mossbauer parameters for lI9Sn in Nb3Sn, Nb6Sn5, and NbSn, for ap- plication in quantitative analysis of superconducting Nb-Sn systems. The NbaSn had an appreciably higher Debye tem- perature. Harrison et al. (136) related the fvs. T data to X-ray structure for a tetraphenylporphinato tin(1V) complex. The crystallographic data were used to obtain absolute f values. A substantial Goldanskii-Karyagin effect was observed and analyzed in terms of vibrational amplitudes. Herber and Katada (139) studied lattice dynamics in iron chloride-graph- ite intercalation compounds. The Debye temperature was lower than in the pure iron chlorides. The ferrous compound had two distinct doublets, one of which did not vary with angle in single crystal experiments. LaPrice and Uhrich (179) ob- tained unusual temperature dependence off in a nematic glass and found evidence for rotational diffusion of diacetylferrocene in the supercooled nematic phase. Weiss and Langhoff (337) used the 58 keV Mossbauer transition from Ij9Tb to probe the one phonon localized modes in TbO,. Using an ultra- centrifuge for velocity scan they found sharp resonances a t 12.3, 14.1, and 16.0 meV, and fit these to a model with localized Einstein terms in addition to the Debye lattice.

Herber and Smelkinson (140) prepared and characterized some Sn(I1) complexes with crown ethers. The compounds with C1- or NCS- have two tin sites, but with C104- a very positive isomer shift and sharp singlet was found with 18- crown-6, indicative of an almost bare Sn2+ ion. The tem- perature variation off for this latter compound was much more drastic than for the compound without the crown ether. Viegers et al. (330) studied lattice dynamics of gold complexes and described a model for the data in terms of inter- and intramolecular vibrational modes. The difference between Au and Sn lattice dynamics in molecular complexes was in- dicated, as was the difference between Au(1) and Au(II1) complexes. Von Eynatten and Bommel (334) studied the f vs. T behavior of iron microcrystals. Two possible explana- tions for the shape of the curves have been proposed-either oscillations of the mcrocrystals or changes in the surface phonon spectrum. Darlington et al. (69) measured elastic and inelastic scattering of j7Fe Mossbauer y-rays from ammonium fluoroberyllate to show that the phasons of the incommen- surate phase do not make large contributions to the Debye- Waller factor. Elastic scattering disappears above the phase transition a t 181 K. Vereshchak et al. (327) studied iron

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oxalates irradiated with y and n. The f value of ferrous oxalate produced by radiolysis from ferric oxalate was higher than the chemically prepared compound. These results are inde- pendent of the nature of radiation. Nascimento and Garg (230) studied the lattice dynamics in FeS04.4H20 single crystals as function of both temperature and crystal orien- tation.

AMORPHOUS MATERIALS The Mdssbauer effect, dependent primarily on short-range

order, is useful in the study of amorphous substances. Among these, materials of particular interest have been metallic glasses and silica glasses.

Among the former, magnetic properties have been of pri- mary concern. Chien and Hasegawa (50) studied the tem- perature dependence of the magnetic field in a number of iron-containing glassy ferromagnets and found the T3/* coefficient to be especially large compared to crystalline materials, indicative of spin-wave excitation. Bayreuther and Lang (27) used conversion electron detection to study the order-disorder transition in thin films of Fe-Co. Commercial metallic glasses were studied with Mossbauer spectroscopy by Franke and Rosenberg (102) and by Gonser et al. (116). In both these, the distribution of hyperfine fields was noted. The former work also studied the effect of heat treatment near the crystallization temperature. The latter authors noted the similarity of field distribution to a liquid structure analog. Vincze and co-workers also studied several aspects of the magnetic field distribution in amorphous metallic glasses. The comparison between Fe,oNi,oB20 and F e d , , (332) shows the effect of Ni substitution is different from that of crystalline alloys. The temperature dependence of field in a commercial sample was determined and interpreted (17). Also Vincze (331) has given a general method to evaluate field distributions in such samples, using the polarization of a small magnet. Litterst et al. (188) determined fields in noncrystalline iron metal as function of temperature for various methods of perparation and noted the nonrandom effects on the hyperfine field from heterogeneity. Tseng e t al. (31 7 ) determined the effect of annealing temperature on the hyperfine field of a metallic glass, finding a strong polarization perpendicular to the ribbon plane a t high annealing temperatures. Fischer et al. (99) studied the polarization effect of an uniaxial tensile stress, using polarized y-rays from a-Fe.

In the general area of silicate glasses, Jach and Nabatian (148) studied the reaction between iron filings and sodium disilicate glass at various temperatures. They found that the reaction in air shows distinct effects of the glass on the oxi- dation of iron. Iwamoto et al. (147) made a detailed Mossbauer study of calcium-iron-silicate glasses, including a determi- nation of the structural sites of iron as function of CaO content and O2 pressure. Mysen and Virgo (227) used Mossbauer spectroscopy to study melt structures in Na(A1,Fe)Si206 as functions of pressure, temperature, and composition, and suggested geochemical implications of their results. Varret and Naudin (325) proposed and tested a method to assay quantitatively the Fe2+/FeJ+ ratio in silicate glasses if the iron is dilute enough to cause paramagnetic structure in Fe3+ a t 77 K.

A number of studies have been reported on borate glasses. Raman et al. (258) measured room temperature spectra of a large number of glasses with Bz03, Fe203, and varying amounts of Na20 and A1203, as well as other alkali metal oxides. Strong variations in isomer shift were correlated with changes in coordination for Fe3+. Also the isomer shift vs. T was used to estimate local specific heats. Sekhon and Kamal (279) studied Bz03 and Na20.2B203 glasses with small amounts of Fe203. In one of the B203 glasses an Fez+ state was found. The magnetic properties of the Fe203 differed in the two types of glass. The Pb0.3B2O,-Fe2O3 system was studied by Burzo and Ardelean (43). In this case all iron was in the matrix even for 50% FezO . Both tetrahedral and octahedral coordination were observed for Fe3+, independent of concentration. Syono et al. (302) measured Mossbauer spectra to 4 K in the BaO- Fe203 system with a small amount Bz03. Low temperature magnetic ordering was observed and interpreted as short-range antiferromagnetism. Among other glasses without B20, or Si02, Laville e t al. (181) found low temperature magnetic ordering in a new homogeneous glass of the system BaO- Fe203-Na20.

van Diepen and Popma (321) studied the temperature dependence of the field in amorphous Fe203. Unlike the metallic glasses, a very slow change was found which fits a spin Brillouin function, even though the field at 0 K was more than expected from spin s/2. Gyorgy et al. (134) report the Mossbauer spectra of amorphous Y3Fe5012. The 4 K spectra show antiferromagnetic ordering with a single field different from that observed in crystalline Y3Fe5012. Among amorphous systems not containing iron should be mentioned the tin oxide reported by Collins et al. (63) and As2Te, Isex studied by Jones and Tse (156). Also, Bowen and Long (42) used orbital population analysis of the lZ1Sb Mossbauer pa- rameters to postulate structures for some amorphous stibonic and stibinic acids.

CATALYSTS AND SURFACES The field of catalysts is quite active and Mossbauer spec-

troscopy continues to make important contributions in this area. The kinetics of CO reduction of NO with an Fe203/A1203 catalyst has been shown by Sokol'skii et al. (289) to be first order in Fez+ concentration, using the Mossbauer effect for determining Fez+. Amelse et al. (8) studied the carburization of SO2-supported iron catalysts at various stages of oxida- tion-reduction and after use in hydrocarbon synthesis. Dezsi e t al. (80) studied Si02-supported Pt-Fe catalysts with dif- ferent iron concentrations with respect to redox behavior. Ludwiczek et al. (200) studied ammonia catalysts of the A1203-promoted type by a variety of techniques, including Mossbauer spectroscopy. Prasada Rao and Menon (257) also used many spectroscopic and other physical techniques, in- cluding Mossbauer, to study the multielement molybdate catalysts for ammoxidation of propylene. Carbucicchio (45) reports Mossbauer studies on supported Fe203-Mo03 catalysts with emphasis on the change in iron state due to interaction with the support. Maksimov et al. (204) determined the effect of bismuth on structural changes in Co-Mo-Fe catalysts used in oxidation of propylene. In a series of papers, Raupp and Delgass- report Mossbauer spectroscopic results on their studies of supported Fe and Fe-Ni catlaysts. First the effect of pretreatment on particle size (260) was studied primarily by the magnetic properties of the alloy. Then two papers followed dealing with Fischer-Tropsch synthesis: a study of the types of carbide phase formed on the catalyst (261) and a paper dealing with the use of constant velocity Mossbauer spec- troscopy to determine rates of carbiding of the catalyst during the synthesis reaction (262). Birchall and Sleight (38) rein- vestigated the catalytic oxides USbO, and USb3010 by lZ1Sb Mossbauer spectroscopy. In contrast to previous work, they found no evidence of unusual covalency in the Sb-0 bonds. However, the two compounds did exhibit a measurable dif- ference in isomer shift.

If scattered conversion electrons are counted, Mossbauer spectroscopy becomes a technique to study solid surfaces. In addition to the more common iron and tin isotopes, this technique was recently applied by Salomon et al. (272) to the study of tantalum metal surfaces using lalTa. Foils had broader lines than single crystals due to adsorbed gas. Huffman and Dunmyre (143) used lI9Sn to study surface properties of tinplate, showing that quantitative thickness determination can be made for oxide coatings up to several hundred angstroms. Sedunov et al. (278) used scattered ra- diation to study surface composition when steel is carburized or carbonitrided: depth selection was effected by counting the scattered y-rays (-1 fim depth) and separately the scattered electrons (-0.1 fim depth). Huffman and Stanley (145) used similar techniques to study Si-sheet steel during annealing in Hz-Nz-HzO atmospheres. Among other types of experiments related to surface properties, Anderson et al. (10) d e ~ o s i t e d . ~ ~ C o on an ultraclean Ni surface and obtained Mossbauer emission spectra, using Auger electron spectroscopy to determine surface contamination. Shechter et al. (282) used transmission Mossbauer spectroscopy to study (in stacks) adsorbed monolayers of butadiene iron tricarbonyl on graphite. Measurements perpendicular and parallel to the film plane were made, and the variation in peak area with temperature was analyzed in terms of diffusion within the film.

Among the more applied areas of surface studies by Mossbauer techniques is corrosion. Blesa et al. (39) used room temperature spectroscopy to characterize the iron oxides in synthetic analogues of nuclear reactor corrosion products.

Ensling et al. (96) used conversion electron detection to study corrosion of steel under boiler conditions. The kinetics of oxide growth were determined. Peev et al. (249) found two distinct iron corrosion products, magnetite and goethite, in the anion exchanger of an industrial desalinizer. Shibuya et al. (284) studied acidic corrosion on tinplate both by con- version electron and transmission 119Sn Mossbauer effect.

There has been a variety of Mossbauer studies of thin films. Some of these have been mentioned earlier. Others of par- ticular note include the study by Bando et al. (19) of iron oxide films prepared by evaporating iron in low pressure oxygen environment, and the work by Haneda and Morrish (135) on surface oxidation of small particles of iron prepared by an aerosol method. van Diepen et al. (322) also studied the oxide layer on iron particles, in this case passivated in 0 2 / N 2 mixture. Several papers have appeared dealing with con- version electron scattering experiments on iron oxide surfaces. Graham et al. (119) studied magnetite films on iron and quantitatively related the spectrum to film thickness in the range up to -3000 A. Tricker (312) reevaluated the cali- bration for thickness determination in iron oxide layers, based on attenuation studies of conversion electrons. Tricker et al. (313) have presented a method to distinguish signals from substrate and surface overlayers in back-scattered 57Fe ra- diation. They used a He/CH, flow counter and evaporated a thin layer of gold on the surface to enhance the photoelectron signal from deep-scattered y-rays.

Duncan et al. (87) studied the variation of magnetic field in thin iron films as function of temperature. For the thinnest films <lo0 8, they found the expected rapid decrease of field with temperature due to spin-wave excitation. However, these films had extrapolated magnetic fields a t T = 0 greater than bulk iron. Hine et al. (141) prepared -100 A thick iron films with the surface layer enriched in j7Fe and coated with thicker layers of various materials. Mossbauer spectra were obtained both at 300 and 4 K, and also in presence of an external field. For MgO and MgF2 coatings an increased field was found, whereas the Sb coating decreased the field. No dead layer was found. Goodwin and Parravano (21 7) studied the kinetics of decarburization in iron films using conversion electron Mossbauer spectroscopy.

Thin film studies with Il9Sn include a study of the passive layer formed on tin in borate buffer solution by Vertes et al. (328) and determination of the composition of tin oxide films produced on glass with sputtering techniques, by Leja et al. (185).

ENVIRONMENTAL STUDIES Environmentally oriented applications of Mossbauer

spectroscopy continue to expand, especially and with obvious reason, in areas related to coal chemistry.

Among the specialized environmental applications is study of meteorites. As examples of this application, Ouseph et al. (237) obtained Mossbauer spectra for several of the iron- containing phases in an iron-nickel meteorite, including taenite and kamacite. The former contains a small amount of a paramagnetic phase, also reported by Albertsen et al. (61, who obtained a series of room temperature spectra from taenite lamellae of an iron meteorite, studied one lamella after progressive surface etching, and one as function of temperature up to 732 K. Three iron phases were found, and the de- struction of the surface-ordered phase was observed at high temperature. Malysheva et al. (205) compared thermal transformations observed in layered silicates with those in a carbonaceous chondrite. The Mossbauer results were inter- preted in terms of the geochemical conditions at which the chondrite was formed. Vdovykhin et al. (326) also studied thermal changes in the iron phases of carbonaceous chondrites, and emphasized the differences between these and ordinary chondrites, concluding that the latter were formed a t higher temperatures and under more reducing conditions.

Geochemical applications to soils have emphasized deter- mination of the type and amount of iron oxide present, with goethite and hematite being the usual forms. Singh et al. (286) performed annealing studies on red and yellow ochre samples, using the high temperature formation of the magnetic he- matite spectrum to distinguish siiperparamagnetic iron oxide from silicate Fe3+. Bigham et al. (37) studied a series of well-oxidized soil clays at room temperature, 77 K, and 4 K. Results from X-ray diffraction and chemical studies were used

ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980 179R

in conjunction with the Mossbauer experiments to characterize the iron oxides as to relative hematite-goethite composition, aluminum substitution, and particle size. Golden et al. ( 1 1 4 , from synthetic samples and soil clays, have established a semiquantitative relation between magnetic field and alu- minum substitution in goethites. Longworth et al. (196) found magnetite in surface soil as a result of forest fires. They used a combination of magnetic methods and Mossbauer spec- troscopy to probe the ferrimagnetic components. Childs et al. (53) studied highly colored New Zealand soils to charac- terize the iron oxides by Mossbauer spectroscopy a t 300 and 77 K. The yellow-brown component has been attributed either to superparamagnetic goethite or to akaganeite. Belozerskii e t al. (30) studied the iron oxide composition of profiles from two distinctly different forest soils.

Studies of environmental samples other than soils include the work by Durrance et al. (90) on the composition of a Permian-Triassic red sandstone from Devon, in which in situ oxidation of Fez+ to Fe3+, with subsequent precipitation of hematite, was found and correlated to climatic changes which had occurred. Also, Cole et al. (60) reported a Mossbauer study of the iron partitioning in Colorado oil shale between carbonate and sulfide phases. Oil-rich shales contained a particularly large variety of both identified and unidentified iron species.

The Mossbauer effect has been applied to studies of lake and ocean sediments. Manning and Ash analyzed the room temperature spectra of sediments from Lake Erie (206) and from a lake in Ontario (207). In both cases the ferrous-ferric ratios were observed to change as function of depth. The high-spin ferrous iron was in the form of chlorite. Ferric iron was presumed to be of the hydrous oxide form. In the Ontario lake, evidence of pyrite was seen. Minai et al. (215) studied the variation from core to rim of a deep ocean basalt by 77 and 293 K Mossbauer spectra, as well as a surface study with an electron scattering detector. Various iron mineral forms were found, with a superparamagnetic form especially prom- inent near the rim. The usefulness of electron scattering detection for surface analysis was indicated both here and in a later paper by Minai and Tominaga (216), in which both air particulates and lake sediments were characterized. I t was noted that air-drying of the sediments affected the oxidation of the iron components. The iron in organic components of sedimentary deposits was characterized by Dickson et al, (82). No organoiron compounds were observed, although it has been

ointed out chemical treatment could have affected such tonding.

Currently, an extremely active environmental application is to the study of coals. Iron is generally present in the form of pyrite, FeS2, although other minerals may be detected. Keisch et al. (165) studied the changes occurring in the pyrite and the nonpyritic iron when coal was hydrogenated a t high temperature and pressure. All the iron was reduced to a pyrrhotite, FeS, with x: - 1.0-1.1. No metallic iron was formed. Huffman and Huggins (144) studied a variety of coal and coke samples to identify the iron phases present, both initially and after high-temperature carburization. A quan- titative method for determining pyritic sulfur in coal from the Mossbauer absorption was presented. Lee et al. (182) have developed the scanning electron microscopy (SEMI analysis of coal minerals and showed how this technique in conjunction with Mossbauer studies can be a powerful combination to study carbonization transformations. Smith et al. (288) ob- tained Mossbauer spectra both a t room temperature and 91 K for a series of coals and coal products, before and after heat treatment. Evidence for a pyrite-coal interaction was found which appeared to be broken when the coal was heated. Jacobs et al. (149) presented a summary of the magnetic and Mossbauer spectroscopic characterization of coal with em- phasis on desulfurization processes. They point out the su- periority of Mossbauer determination of pyrite to wet chemical methods. Russell and Montan0 (269) obtained Mossbauer spectra of iron minerals contained in coal down to 4 K, with emphasis on the magnetic field properties. Stiller et al. (300) used Mossbauer spectra of coal seams to evaluate its appli- cation in predicting acid mine drainage potential. This latter has been shown to be correlated with the presence of water- soluble FeS04.H20 in the coal.

Among other studies of naturally occurring iron minerals is the work of Parkin e t al. (242) on the intervalence charge

180R ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980

transfer in blue gem minerals. Significant amounts of Fez+ were found in octahedral sites replacing A13+. Chandra et al. (47) studied the angular variation of Mossbauer absorption in single crystals of biotite in a search for anisotropy. No such GoldanskiikKaryagin effect was observed. Mineeva (21 7) used point change calculations of the electric field gradient in biotites to relate defect structure to spectral effects. He found the Fe3+ field gradient is essentially the same a t the two octahedral sites, whereas adjacent defects produce large differences in gradient. The conclusion is that there is no simple correlation between number of Mossbauer doublets and number of nonequivalent sites.

Johnston and Glasby (154) obtained precision room tem- perature spectra of iron-manganese nodules and analyzed these in terms of the iron oxide-hydroxide mineralogy. Na- lovic and Janot (229) used Mossbauer spectroscopy, both a t room and low temperatures to study the crystallization of iron hydroxides with emphasis on simulating environmental con- ditions.

Tominaga et al. (309) have characterized ancient roofing tiles by their Mossbauer spectra, correlating the iron oxidation state with color and with method of production. Longworth and Warren (199) found correlation between the Mossbauer spectra of various archeological samples of obsidian and their geological sources. A number of applications to archaeology were reported a t the Kyoto conference (320).

P H A S E TRANSITIONS A N D ANALYSIS Quantitative analysis of iron in different sites is not gen-

erally possible due to different recoil-free fractions. Collins (61) has outlined a simple method based on data obtained a t several temperatures which eliminates this error. Bahgat (15) has extended this method to include absorber thickness corrections. DeSitter et al. (77) have applied Mossbauer spectroscopy quantitatively to the mineral composition of industrial iron ore sinters. Kalyamin et al. (159) have shown that liquid nitrogen temperature provides an equivalent re- coil-free fraction for Fe3+ frozen solutions of different chemical nature. Peev et al. (248) used the Mossbauer spectra of Fe3+ deposited on Al,03 to determine quantitatively the a- and r-A1203 ratios.

Phase transitions may be studied with precision using the techniques proposed by Jaggi (150). The glass transition in propane-1,2-diol was studied by Fez+ Mossbauer effect in dilute solution by Litterst et al. (189). Takeda et al. (303) prepared and characterized stoichiometric CaFe03 showing by Mossbauer studies that a charge disproportionation from Fe4+ to Fe3+ + Fe5+ is associated with the phase transition a t 115 K. Townsend et al. (310) studied the details of the 475 K ferrimagnetic transition in single crystals of Feo,& Mossbauer diffraction of the j7Fe y-ray was used to study critical scattering a t the phase transition in RbCaF, by Maetz et al. (203). Trooster and de Valk (315) obtained Mossbauer data on single crystals of FeI, and FeBr,, including data in the presence of an external field. Their emphasis was on the antiferromagnetic-paramagnetic transition, and they have presented evidence that in FeI, this transition is first order.

Identification of phases in complex mixtures is a natural use of Mossbauer spectroscopy. Cohen et al. (59) identified tin metal as predominate in tin-anodized aluminum. Leid- heiser et al. (183) studied Mossbauer spectra of thermally prepared nickel-tin alloys and compared these to electrode- posited NiSn. Leidheiser et al. (184) studied the Mossbauer emission spectra of cobalt-hardened gold electrodeposits. These systems were also studied independently by Cohen et al. (56).

Berry and Maddock (35) used conversion electron Mossbauer spectroscopy to determine the nature of the surface formed on iron metal during phosphating processes for cor- rosion protection. A large number of phases were detected by Mossbauer and X-ray techniques from the thermal de- composition of K4Fe(CN)g3H20 by Kunrath et al. (174). Kopcewicz and Kotlicki ( 1 71) studied the chemical changes in ferrocene during proton irradiation of ferrocene. Tominaga and Sato (275, 308) determined the effects of photolysis on bis- and trisoxalate iron(II1) complexes both in pure solid form and in solution. Scattered electron detection was used (308) to indicate that photolysis is more nearly complete a t the surface. In an unusual application of 237Np Mossbauer spectroscopy, Karraker and Stone (163) studied the reaction

product from NpI, reaction with K2CBH8 and its properties. General application of Mossbauer spectroscopy to phase analysis was discussed by Nikolaev et al. (232), in which a method was proposed for analysis of phases which does not require temperature studies or the assumption of equal re- coil-free fractions. The Morin transition between weak fer- romagnetism and antiferromagnetic behavior in hematite has been the subject of a detailed investigation by Nininger and Schroeer (234). This work included restudy of the effect of particle size on the transition. Povitskii et al. (256) determined the effect of A1 impurity on the Morin transition in hematite.

Specialized equipment allows Mossbauer spectra to be obtained at high pressure. The effect of pressure on the hyperfine interactions is of theoretical significance. Also, the technique provides a unique tool for investigating high pressure phase transitions. Abd Elmegid and Kaindl ( 1 ) studied europium intermetallic compounds at 4 K up to 60 kbar. The variation with pressure of both the isomer shift and magnetic field were obtained. Unlike the metal itself, most of the compounds have negative values of dH/dp. Moser et al. (222) obtained high pressure spectra of 151Eu and I19Sn in EuS and EuSe, observing the change with pressure of the Curie temperature. Nikolaev et al. (233) determined the magnetic fields a t Fe and Sn in FeSn, up to 14 kbar. Both isotopes have similar T and p dependence. Amthauer et al. (9) studied the high pressure 9Sn spectra of the mixed valence compound Sn,S3. The two tin sites have quite different Debye temperatures and different pressure effects on the isomer shift. Karger et al. (162) used '%Au as a probe for studying the PdH, and Pdl_,Ag, systems. Among other types of Mossbauer experiments, the effect of pressure on isomer shift was de- termined. Williamson et al. (340) made theoretical calculations of the pressure dependence of electron density for the elements Ag-Te, and compared these calculations with experimental results on Sn and Sb. Kapitanov and Yakovlev (161) studied the phase transition in Mg,Sn under high hydrostatic pressure.

S P I N TRANSITIONS AND ELECTRON EXCHANGE

Continued reports appear on high spin-low spin transitions in iron complexes. Zimmermann and Konig (345) developed a model for these transitions which includes the effect of lattice vibrations as well as the low symmetry ligand field and spin-orbit coupling. This model was applied to experimental data for Fe (4,7-(CH3!2-phen)2!NCS)2., Ritter et al. (265) has shown in one high spin-low spin transition that the previous sample history and length of time for cooling affected the kinetics of transformation. Gutlich et al. (132) studied dilution effects on the spin transition in Fe,Znl , ( 2 - P i ~ ) ~ C l ~ . The iron spin transition occurred even for very low values of x , although changes in transition temperature were observed. Gutlich et al. (130) presented a general thermodynamic model for in- terpreting high spin-low spin transitions and applied the model to the experimental results above. The model yields an effective cooperative domain size, as well as separating entropy and enthalpy effects.

Mossbauer spectroscopy has been used to study electron exchange processes in a number of mixed valence iron com- pounds. As examples of these, Grandjean and Gerard have reported studies of the spinels Znl .Ge,Fe204 (121) and CuCr,-,Fe,O, (111). In the former case the iron was found on the B site only throughout the series, but a broad exchange doublet was observed at room temperature for x = 0.25, 0.5, and 0.75. Magnetic ordering occurred below room temperature for x = 0.25 and 0.5. The CuCr,O, spinel, with Fe on the A sites, was studied between 77 and 873 K. Small amounts of Fez+ were observed in addition to Fe", and explained in terms of a band model and electron exchange. Nolet and Burns (235) studied electron delocalization in the silicate mineral ilvaite by Mossbauer spectroscopy over a wide range of temperature. They reported doublets associated with electron delocalization observed even at 80 K, and proposed a thermal activation model to explain the results, as opposed to a Verwey-type transition. Seregin et al. (280) studied the Mosshauer emission spectra of iron substituted in GaAs and GaP with differing impurity concentrations. Distinctly different isomer shifts were observed with p- or n-type semiconductors, corresponding to neutral or negatively charged iron species. A dependence of isomer shift on the Fermi level was found in Gap, with fast exchange occurring between the two valance states. Moto-

yama et al. (224) studied a series of mixed- and average-va- lance ferrocene derivatives. The influence of the conjugated K systems was noted.

Mixed valence compounds of antimony have been studied using '"Sb Mossbauer spectroscopy by Donaldson and Thomas (84, 85) and by de Jesus Filho et al. (75). In the former work, the spectra were interpreted as indicating loss of Sb3+ electron density into solid state bands. The latter paper emphasized that no evidence of electron exchange was found up to 140 K.

MATERIALS STUDIES A number of applications of the technique to the study of

polymeric materials have appeared. Kessler et al. (166) studied changes occurring on stannous capronate catalyst during the polymerization of formaldehyde. They interpreted their re- sults as indicating a number of three-coordinate complexes formed as intermediates. Ford and Sams (101 1 observed by Mossbauer effect the polymerization of a long-standing sample of triphenyltin trichloroacetate. Imshennik et al. (146) re- ported Mossbauer studies of €'e3+ in polyacrylic acid, in particular magnetic ordering at low temperature and the effect of iron concentration on this ordering. At 3% iron, clustering was observed. Meyer and Pinei-i (214) studied the form of iron clusters in a butadiene-styrene-vinylpyridine terpolymer cross-linked with FeCl, by Mossbauer, magnetization, and X-ray scattering measurements. Three distinct iron complexes were observed in the variable temperature Mossbauer spectra: iron clusters, dimers, and almost isolated ferric species. Tripathi et al. (314) reported preliminary Mossbauer studies on poly(iron methacrylate). Allcock et al. (7) used Mossbauer spectroscopy to characterize the state of iron porphyrins in several water-soluble polymers 0:' poly(aminophosphazenes), particularly in relation to O2 and CO binding.

The important industrial material steel has naturally been studied extensively by Mossbauer spectroscopy. Many aspects of steel treatment are uniquely investigated by this technique. Belozerskii e t al. (31) developed a mathematical model and applied it to secondary hardening processes in low-carbon steel. Edwards et al. (93) studied the temper embrittlement in steel by l19Sn Mossbauer spectroscopy. Gridnev et al. (122) studied a t 65 K the 5'Fe spectra of cold-worked steel. De- Cristofaro et al (73) determined the kinetics of carbon clus- tering in martensitic steels, using Mdssbauer spectroscopy. Solomon and Levinson (290) used 57Fe Mossbauer spectra to study the 475 "C embrittlement of stainless steels. Syn et al. (301) used both Mossbauer and electron microscopy to study the mechanical stability of austenite in tempered 9 Ni steel. Tenuta Azevedo and da Silva (306) studied austenite in a low carbon alloy steel. Williamson et al. (341) reported the de- termination of small amounts of austenite and carbide in hardened medium carbon steels Wickberg and Eck (339) studied proton radiation damage to 310 stainless steel by Coulomb excitation Mossbauer cffect.

CHEMICAL STUDIES-IRON In this section we reference those papers dealing with 57Fe

Mossbauer effect which have a chemical emphasis, but which were not appropriately referenced in the earlier sections. The following section includes significant papers dealing with isotopes other than iron.

Chambaere et al. (46) performelj high-resolution studies of synthetic 8-FeOOH (akaganeite) a t room temperature, showing clearly two discrete doublets, one due to the presence of halogen ions in the structure. Galeczki and Hirsch (107) studied the low temperature (7-17 K) spectra of magnetite and proposed an alternative explanation of its spectra. Spencer et al. (292) considered cation distributions of iron in spinels as determined by Mossbauer spectroscopy, and showed t,hat the usual forms of ligand field theory did not account for the results. Stiller et al. (299) prepared and characterized by its Miissbauer spectrum a binary iron sulfide, Fe,S,, ob- serving antiferromagnetic ordering at 4 K, and also a trans- formation around room temperature. Anhydrous ferric sulfate was characterized by Long et al. (195) using Mdssbauer spectra, magnetic susceptibility, and neutron diffraction.

Of note in organoiron studies in which Mossbauer spec- troscopy is emphasized is the temperature and external field study of S = 1 ferrous tetraphenylporphyrin by Lang et al. (176). The data were interpreted by a crystal field model.

ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980 181 R

Wong et al. (343) used external fields a t 4 K to study the Mossbauer spectra of cubane-type iron cluster compounds, as well as determining magnetic susceptibilities, with the objective of elucidating electronic structure. Dolphin et al. (83) obtained low temperature Mossbauer spectra with and without applied magnetic field of Fe(II1) complexes with octaethylporphyrin and tetraphenylporphine. No Goldan- skii-Karyagin effect was observed. Long et al. (194) studied the bonding in cyclopentadienyliron carbonyl complexes using Mossbauer spectroscopy. Latorre et al. (280) determined thermodynamic and kinetic parameters for the isomerization in Fez+ thiourea complexes by means of their Mossbauer spectra.

CHEMICAL STUDIES-OTHER ISOTOPES Collins and Benczer-Koller (62) have made precision

measurements of the quadrupole interaction in tin metal from 4 to 450 K. Comparison was made with calculated field gradients. Corvan and Zuckerman (64) examined the Mossbauer spectra of tin(I1) amines with particular emphasis on explaining why some of these are so highly colored. A correlation of Mossbauer parameters with the property of color was obtained. Dance and Jones (66) have continued the 12Te study of organotellurium compounds, in this paper empha- sizing heterocyclic compounds. Davies et al. (72) have pro- posed that the quadrupole splitting observed in metal halide complexes of (p-EtoC6H4),Te may provide a scale of Lewis acidit?. Kim and Boolchand (167) combined 1291 source data from 29mTe-labeled Te,Sl_, and Te,Sel-, with previous '*Te absorber measurements to elucidate the chemical bonding. Friedt and Sanchez (105) used lZgI spectra in an external field to study the transferred interna! field at iodine in G I 3 . Friedt e t al. (103) have studied chemical bonding and magnetic properties of several R,NFeI, complexes by combined 5'Fe and lZ9I Mossbauer effect.

Yarmarkin e t al. (344) used 57Fe and IZ1Sb Mossbauer spectroscopy to study these respective impurity metals in semiconducting and insulating Ti02. The S b was always present as Sb5+, whereas the Fe state varied depending on the conditions. Stevens and Trooster (298) obtained 121Sb Mossbauer spectra of a series of antimony dithiocarbamate complexes and discussed these results in terms of structure and bonding variations in the series. DeWaard et al. (78) have made the most extensive study of xenon compounds by "'Xe Mossbauer effect. Twenty-one compounds were investigated, covering four valence states. Isomer shifts variations were small, but trends could be distinguished. The quadrupole s littings provided the primary chemical information. The

effect has been used to determine quadrupole splitting in a complex of Ni(I1) by Dale et al. (65), the first such splitting reported for that geometry. Goring et al. (118) determined the 61Ni hyperfine parameters as function of temperature for the spinel NiCrz04, fitting the magnetic field data to a spin S = 1 curve.

Coordination in gold(1) complexes with Ph3P was the subject of a lg7Au Mossbauer study by Parish and Rush (241 ). Large variations in isomer shift occurred with coordination number. Quadrupole coupling variations were in agreement with the point charge model. A new synthesis of gold cluster compounds of the type Aull(PR&X3 and Mossbauer studies of these were reported by Vollenbroek et al. (333). The Mossbauer spectra showed clearly more than one distinct type of Au, although overlapping peaks required certain constraints to fit the five known crystallographic sites.

Cohen et al. (58) studied the effect of cycling on H2 storage in EuRh,, using lslEu Mossbauer spectra to characterize the changes in metal environment. Dunlap et al. (89) used the '"Yb Mossbauer effect in external fields a t low temperature to evaluate crystal field parameters for YbzTiz07. Afanas'ev e t al. (4) used the same isotope to study Cs2NaYbC1,. Their work developed the relation between theoretical spin-spin relaxation line shape and the experimental spectrum, showing that the frequency dependence of relaxation rate could be evaluated from the observed spectrum.

MISCELLANEOUS APPLICATIONS

P Ni Mossbauer "

Several articles have appeared recently which have direct medical applications. Guest (126) has continued his inves- tigations on human lungs, using Mossbauer spectroscopy to

182R ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980

determine the amount of endogeneous iron present for lungs with bronchitis vs. normal lungs. Another interesting study is a comparison of thalassemic heart tissue with normal heart tissue. This has been reported by two independent groups (26,239), both finding that the red blood cells of thalassemic tissue give Mossbauer spectra which are similar to those ob- tained from ferritin.

Kopcewicz and Kopcewicz (1 70) have continued their study of iron sources in atmospheric air. By varying the tempera- tures of their Mossbauer samples, they were able to determine the sizes of the particles and suggest industrial air pollution as a significant contributor to the iron concentration in air. In another study Eymery and others (98) have used Mossbauer spectroscopy to investigate iron compounds in car exhaust. The iron basically a pears as 0-Fe203 in the form of ultrafine particles of -120 8: diameter.

ACKNOWLEDGMENT

The completion of this review would have been impossible without Virginia E. Stevens, who assisted extensively with retrieving and organizing the literature, proofreading, and typing. Also assisting with typing were Mary Jane Winfrey and Joyce Weatherspoon.

LITERATURE CITED

(1) Abd El.megid, M. M.. Kaindi, G., Hyperfine Interac.. 4, 420 (1978). (2) Abe, M., Kaneta, K., Uchino, K., J . Phys. Soc. Jpn. 44, 1739 (1978). (3) Afanas'ev, A. M., Gorobchenko, V. D., Peregudov. V. N., Hyperfine Interac.,

(4) Afanas'ev, A. M. Onishchenko E. V.. Asch, L., Kalvius, G. M., Phys.. Rev. 5, 469 (1978).

Lett. 40, 816 (1978).

585 11978). (5) Afanas'ev, A. M., Onishchenko E. V., Sov. Phys.-J€TP(€ng/. Transl.), 47,

(6) Albertsen, J. F., Aydin, M., Knudsen, J. M., Phys. Scr . , 17, 467 (1978). (7) Allcock, H. R., Gteigger, P. P., Gardner, J. E., Schmutz. J. L., J . Am. Chem.

(8) Amelse, J. A. Butt, J. E., Schwartz, L. H., J. Phys. Chem., 82, 558 (1978). (9) Amthauer, G., Fenner, J., Hafner, S. S., Holzapfel, W. B., Keller, R., J .

Chem. Phys.. 70, 4837 (1979). (10) Anderson, C. R.. Richards, B. G., Hoffman, R. W., Thin SojidF;/ms, 58,

SOC., 101, 606 (1979).

235 (1979).

16. 466 119791. (11) Anderson, C. R., Richards, B. G., Hoffman, R. W., J . Vac. Sci. Techno/.,

(12) Artem"ev, A. N., Aleshin, K. P., Sklyarevskii, V. V., Stepanov, E. P., Instrum. Exp. Tech. USSR (Engl. Transl.), 21, 924 (1978).

(13) Artem'ev, A. N., Kabannik, V. A. Kazakov, Yu. N., Kulipanov. G. N., Meleshko,' E. A., Sklyarevskii, V. V., Skrinskii, A. N., Stepanov, E. P., Khlestov, V. B.. Chechin, A. I., Nucl. Instrum. Methods, 152, 235 (1978).

(14) Asch, L., Potzel, W.. Kaivius, G. M., Spirlet, J. C., Muller, W., Hyperfine Interact., 5, 457 (1978).

(15) Bahgat, A. A., Phys. Status SolidiA, 52, K217 (1979). (16) Baldwin, G. C., Nucl. Instrum. Methods, 159, 309 (1979). (17) Balogh, J., Vincze, I . , Solid State Commun., 25, 695 (1978). (18) Bancroft, G. M., J . Phys. (Paris), Colloq., 40, C2-464 (1979). (19) Bando, Y., Hori, S., Takada, T. , Jpn. J . App/. Phys., 17, 1037 (1978). (20) Banerjee. S., Phys. Rev. B , 19, 5463 (1979). (21) Banerjee, S., Blume, M., Phys. Rev. B , 16, 3061 (1977). (22) Barb, D., Tarina, D., Ed., "Proceedings of the International Conference

on Mossbauer Spectroscopy, Volume 2", Documentation Office, Central Institute of Physics, Bucharest, 1978, 304 pages.

(23) Barrett, P. H., Pasternak, M., Pearson, R. G., J . Am. Chem. SOC., 101,

(24) Bashkirov, Sh. Sh., Belyanin, A. L., Sadykov, E. K., Phys. Status Solidi

(25) Bashkirov, Sh. Sh., Sadykov. E. K., Sov. Phys.-Solid State(€ngl. Transl.),

222 (1979).

8 , 93, 437 (1979).

20, 1988 (1978):

(Paris). Calloo.. 40. C2-502 (1979). (26) Bauminger, E. R., Cohen, S. G., Ofer, S., Rachmilewitz, E. A,, J . Phys.

(27) Bayreuther,'G., Lang, B., J . Magn. Magn. Mater., 9, 1 1 (1978). (28) Belozerskii, G. N., Pbys. Status Solidi A , 46, 131 (1978). (29) Belozerskii, G. N., Gorobachevskii, S. N.. "Proceedings of the International

Conference on Mossbauer Spectroscopy, Volume l", D. Barb, D. Tarina, Ed., Documentation Office, Central Institute of Physics, Bucharest, 1977, p 225.

(30) Belozerskii, G. N.. Kazakov, M. I . , Gagarina. E. I.. Khantulev, A. A,, Pochvovedenie. No. 9, 35 (1978).

(31) Belozerskii, G. N., Yerkin, V. M., Malyshevskii. V. A,, Sokolov. 0. G., Sosenushkin, Ye. M., Khimich, Yu. P., P w s . Met. Metallogr. USSR(€ngi. Transl.), 43(1), 124-30 (1977).

(32) Bender, O., Schroeder, K., Phys. Rev. 6. 19, 3399 (1979). (33) Berry, F. J., "Advance in Inorganic Chemistry and Radiochemistry, Volume

21", J. Emeleus, A . G. Sharpe, Ed., Academic Press, New York, 1978, p 255.

(34) Berry, F J., Transition Met. Chem., 4, 209 (1979). (35) Berry, F. J., Maddock, A. G.. J . Chem. Soc., Chem. Commun., 308

(36) Best, K. J., Rothe, E., Cryogenics, 19. 73 (1979). (37) Bigham, J. M., Golden, D. C., Bowen, L. H.. Buol. S. W., Weed, S. B., Soil

(38) Birchail, T., Sleight, A,, J . Catal., 53, 280 (1978).

(1978).

Sci. Soc. Am. J . , 42, 816 (1978).

(39) Blesa, M. A., Maroto, A. J. G., Passaggio, S. I . , Labenski, F., Saragovi-

(40) Bonchev, Ts., Minkova, A,, Kushev, G., Grozdanov, M., Nucl. Insfrum.

(41) Bowen, L. H., Mossbauer Eff. Ref. Data J . , 2, 76 (1979). (42) Bowen, L., H., Long, G. G., Inorg. Chem., 17, 551 (1978). (43) Burzo, E., Ardelean, I . , Phys. Chem. Glasses, 20, 15 (1979). (44) Carbucicchio, M., Nucl, Instrum. Methods, 144, 225 (1977). (45) Carbucicchio, M., J. Chem. Phys., 70, 784 (1979). (46) Chambaere, D., Govaert, A., deSitter, J.. deGrave. E., Solid State Com-

(47) Chandra, R., Tripathi, R. P., Lokanathan, S.. Phys. Status Solidi B , 88,

(48) Chappert, J.. J. Phys. (Paris), Colloq., 40, C2-107 (1979). (49) Chappert, J., Teillet, J., Varret, F., J. Magn. Magn. Mater., 11, 200 (1979). (50) Chien. C. L., Hasegawa, R., Phys. Rev. 6, 18, 2115 (1977). (51) Chien, C. L., Musser, D., Gyorgy, E. M., Sherwood, R. C., Chen. H. S.

(52) Chien, C. L., Walker, J. C., Shnidman, R., Phys. Rev. B, 19, 1363 (1979). (53) Childs, C. W., Goodman, B. A., Churchman, G. J., "International Clay

Conference 1978", M. M. Mortland, V. C. Farmer, Ed., Elsevier, Amsterdam, 1979, p 555.

(54) Chow, Y. W., Fuchs. M., Mukerji, A., J . Phys. (Paris), Colloq., 40, C1-41

(55) Clausen, B. S., M h p , S., Nielsen, P., Thrane, N., Topsde, H., J. Phys.

(56) Cohen. R. L., Koch, F. B., Schoenberg, L. N., West, K. W., J. Hectrochem.

(57) Cohen. R. L., Miller, G. L., West, K . W., Phys. Rev. Left., 41, 381 (1978). (58) Cohen, R. L., West, K. W., Buschow, K. H. J., Solid State Commun., 25,

(59) Cohen, R. L., Raub, C. J., Muramaki, T., J . Electrochem. Soc., 125, 34

(60) Cole, R. D.. Liu, J. H., Smith, G. V., Hinckley, C. C., Saporoschenko, M.,

(61) Collins, R. L.. Phys. Len.. 66A, 153 (1978). (62) Collins, G. S., Benczer-Koller, N., Phys, Rev. B , 17, 2085 (1978). (63) Collins, G. S., Kachnowski. T., Benczer-Koller. N., Pasternak, M.. Phvs.

Badler, C., Radiat. Phys. Chem., 11. 321 (1978).

Methods, 147, 481 (1977).

mun., 26, 657 (1978).

633 (1978).

Luborsky, F. E., Walter, J. L.. Phys. Rev. B, 20, 283 (1979).

(1979).

E , 12, 439 (1979).

Soc., 126, 1608 (1979).

293 (1978).

( 197 8).

fuel, 57, 514 (1978).

Rev. 6 , 19, 1369 (1979). (64) Corvan. P. J., Zuckerman, J. J., Inorg. Chim. Acta, 34, L255 (1979). (65) Dale, B. W., Dickinson. R. J., Parish, R. V.. Chem. Phys. Lett., 64, 375

11979). (66) Dance, N. S., Jones, C. H. W., Can. J , Chem., 56, 1746 (1978). (67) Daniels, J. M., Can. J . Phys., 57, 263 (1979). (68) Danon, J., Scorzelli, R. B., Pollak, H., "Proceedings of the International

Conference On Mossbauer Spectroscopy, Volume 2". D. Barb, D. Tarina, Ed., Documentation Office, Central Institute of Physics, Bucharest, 1978, p 217.

(69) Darlington, C. N. W.. Kitching, S. A.. O'Connor. D. A.. Phys. Rev. Lett.,

(70) Dattagupta. S.. Phys. Rev. B , 18, 158 (1977). (71) Dattagupta. S., Hyperfine Interac., 4, 942 (1978). (72) Davies, I., McWhinnie, W. R., Dance, N. S., Jones, C. H. W.. Inorg. Chim.

(73) DeCristofaro, N., Kaplow, R., Owen, W. S.. Metall. Trans. A , 9A, 821

(74) de Grave, E., Chambaere, D., de Sitter, J., Govaert. A,. Solid State

(75) de Jesus Filho, M. F., Sanchez. J. P., Friedt, J. M., Phys. Status Solidi

(76) Delyagin. N. N . , Zonnenberg. Yu. D., Nesterov. V. I . , Sergeev, S. A,. Instrum. f x p . Tech. USSR (Engl. Transl.), 20, 660 (1977).

(77) de Sitter, J., Govaert, A., de Grave, E., Chambaere, D., Bull. SOC. Chim. Selg. 88, 841 (1977).

(78) de Waard. H., Bukshpan, S., Schrobilgen, G. J., Holloway, J. H., Martin, D., J. Chem. Phys., 70, 3247 (1979).

(79) de Waard, H., Reintsema, S. R., Hyperfine Interac., 4, 720 (1978). (80) Dezsi, I . , Nagy, D. L., Eszterle, M., Guczi, L.. React, Kinet. Catal. Lett.,

8, 301 (1978). (81) Dickson, D. P. E., "Amino-Acids, Peptides, and Proteins, Volume 9," R.

C. Sheppard, Ed., The Chemical Society, London, 1979, p 265. (82) Dickson, D. P. E., Heller-Kallai. L., Rozenson. I., Geochim. Cosmochim.

Acta 43, 1449 (1979). (83) Dolphin, D., Sams, J. R., Tsin, T. E., Wong, K. L., J . Am. Chem. Soc.,

100, 1711 (1978). (84) Donaldson, J. D., Thomas, M. J. K., Radiochem. Radioanal. Left., 33, 219

(1978). (85) Donaldson, J. D., Thomas, M. J. K., Inorg. Nucl. Chem. Lett., 14, 93

(1978). (86) Donaldson, J. D., Tricker, M. J., "Spectrtoscopic Properties of Inorganic

and Organometallic Compounds, Volume lo" , N. N. Greenwood, Ed., The Chemical Society, London, 1977, p 360.

(87) Duncan, S.. Owens, A. H., Semper, R. J., Walker, J. C., Hyperfine Interac.,

42, 1296 (1979).

Acta, 29, L203 (1978).

( 19 78).

Commun., 25, 17 (1978).

6, 91, 443 (1979).

4. 886 (19781. 1 - - I

(88)'Dinham, W. R., Wu, C. T , Polichar, R. M , Sands, R. H , Nucl. Instrum Methods, 145. 537 11977)

(89) Dunlap, 8. D., Shenoy, G. K.. Friedt, J. M., Meyer. M., McCarthy, G. J..

(90) Durrance, E. M., Meads, R. E., Ballard, R. R. B., Walsh. J. N., Geol. SOC.

(91) Dyson, W., Montano, P. A . , J Am. Chem. SOC., 100, 7439 (1978). (92) Dzyublik, A. Ya., Ukr. f i z . Zh. (Russ. Ed.) , 23, 881 (1978). (93) Edwards, B. C., Eyre, 8. L., Cranshaw, T. E., Nature, 269, 47 (1977). (94) Elsukov. E. P.. Startseva, I. E., Phys. Met. Metallogr. USSR(€ngl. Transl),

J . Appl. Phys., 49, 1448 (1978).

Am. Bull.. 89, 1231 (1978).

44(2), 29 (1977).

(95) Elwenspoek, M., Sohisch, M., Qukmann, D., Mol. phys., 35, 1221 (1978). (96) Ensling, J., Fleisch J.. Grimm, Fleisch, R., Gruber, J., Gutlich, P., Coros.

Sci., 18; 797 (1978). (97) 119791. Ernst, H., Koch, W., Wagner, F. E., Bucher, E., Phys. Left., 70A, 246

(98j Eymery, J. P., Raju, S. B., Maine, P., J. Phys. D , 11. 2147 (1978). (99) Fischer, H., Gonser, U., Preston, R. S., Wagner, H. G., J . Magn. Magn.

(100) Foct, J., LeCaer, G., Bull. Cercle, Etud. Met., 13, 381 (1977). (101) Ford, B. F. E., Sams. J. R., Inorg. Chlm. Acta. 28, L173 (1978). (102) Franke, H., Rosenberg, M., J . Magn. Magn. Mater., 7, 168 (1978). (103) Friedt. J. M., Petridis, D., Sanchez, J. P., Reschke, R.. Trautwein, A,,

(104) Friedt, J. M., Poinsot. R.. Rebizant, J.. Muller, W.. J . Phvs. Chem. Solids,

Mater., 9. 336 (1978).

Phys. Rev. 6, 19, 360 (1979).

40, 279 (1979) (105) Friedt, J M I Sanchez, J P I J Phys C , 11, 3731 (1978) (106) Friedt, J M , Shenoy, G K , Pages, M , J Phys Chem Sol&, 39, 1313

11978) (107) &leczki, G., Hirsch, A. A,, J . Magn. Magn. Mater., 7, 230 (1978). (108) Garg, R., Oliveira, A. C., Garg, V. K., Phys. Status Solidi 6, 84, K17

(109) Gavrilov, B. M.. Zemskov, B. G., Nucl. Instrum. Methods, 158, 531

(1 10) Genand-Riondet, N., Imbert, P., Lericque, J. F., Rev. Sci. Instrum., 49,

(111) Gerard, A., Grandjean, F., J. Phys. C , 12, 4601 (1979). (1 12) Gerdau, E., Winkler, H., Sabathil, F., "AIP Conference Proceedings, No.

Workshop on New Directions in Mossbauer Spectroscopy", G. J.

(113) Gibb, T. C.. J . Chem. Soc., Dalton Trans.. 743 (1978). (114) Golden, D. C., Bowen. L. H.. Weed. S. B.. Biaham. J. M.. SoilSci. SOC.

(1977).

(1979).

606 (1978).

38: Perlow, Ed., American Institute of Physics, New York, 1977, p 35.

Am J , 43, 802 (1979) (115) Goldstein, F S , Peierls, R , J Phys C , 11, 1921 (1978) (116) Gonser, U , Ghafari, M , Wagner, H G , J Magn Magn Mater, 8, 175

119781 (117) Goodwin, J. G., Jr., Parravano, G., J . Phys. Chem., 82, 1040 (1978). (118) Goring, J., Wurtinger. W., Link, R., J. Appl. Phys.. 49, 269 (1978). (119) Graham, M. J.. Mitchell, D. F.. Channing, D. A,. Oxid. Met.. 12, 247

(120) Graham, M. J., Mitchell, D. F., Phillips, J. R., Nucl. Instrum. Methods,

(121) Grandjean, F., Gerard, A., Solid State Commun., 25, 679 (1978). (122) Gfklnev, V. N., Gavrihuk, V. G., Razumov, 0. N.. Sov. Phys.-Dokl. (€nul.

(1978).

141, 131 (1977).

Trans, ), 22, 519 (1977) (123) Grow, J M I Howard, D G , Nussbaum, R H , Takeo, M , Phys Rev

B 17 15 11978) (124) Grozdanov, M'., Bonchev, Ts., Georgiev, G. T.. Dokl. Akad. Nauk. Bolg.,

(125) Grozdanov, M., Bonchev, Ts., Georgiev, G. T., Bulg. J. Phys., 5, 443

(126) Guest, L., Ann. Occup. Hyg,. 21, 151 (1978). (127) Gupta, G. P., Dickson, D. P. E., Johnson, C. E., J . Phys. C , 12, 2419

(128) GuDta, M. P., Kanetkar. S. M.. Date. S. K.. Niaavekar. A. S.. Sinha. A.

31, 1271 (1978).

(1 978).

(1979).

P. E., 2, Phys. C , 12, 2401 (1979). (129) Gutlich, P., J . Phys. (Paris), Colloq., 40, C2-378 (1979). (130) Gutlich, P., Koppen, H., Link, R., Steinhauser, H. G., J . Chem. Phys.,

70. 3977 11979). (131)'Gutlich, P., Link, R., Fritsch, T., Wolf, G. K., Nucl. Instrum. Methods,

(132) Gutlich. P., Link, R., Steinhauser, H. G.. Inorg. Chem., 17, 2509 (1978). (133) Gutlich, P., Link, R., Trautwein, A., Ed., "Mossbauer Spectroscopy and

Transition Metal Chemistry", Springer-Veriag, Berlin, 1978, 320 pages. (134) Gyorgy, E. M., Nassau, K., Eibschutz, M.. Waszczak, J. V., Wang, C.

A . , Shelton. J. C.. J . ADD/. Phvs.. 50, 2883 (1979).

148, 573 (1978).

(135) Haneda. K.. Morrish,'A. H.; Surf. Sci., 77, 584 (1978). (136) Harrison, P. G., Molloy, K., Thornton. E. W., Inorg. Chim. Acta, 33, 137

(137) Hartmann-Boutron. E., J. Phys. (Paris), 40, 57 (1979). (138) Henry, M., Varret. F., Phys. Status Solidi A , 44, 601 (1977). (139) Herber, R. H.. Katada, M., J . Inorg. Nucl. Chem., 41, 1097 (1979). (140) Herber, R. H., Smelkinson. A. E., Inorg. Chem.. 17, 1023 (1979). (141) Hine, S., Shinjo, T., Takada, T., J . Phys. SOC. Jpn., 47, 767 (1979). (142) Hirvonen, M. T., Nucl. Instrum. Methods, 185, 67 (1979). (143) Huffman, G. P., Dunmyre, G. R., J. Electrochem. Soc., 125. 1652 (1978). (144) Huffman, G. P., Huggins, F. E., Fuel, 57, 592 (1978). (145) Huffman, G. P., Stanley, E. E., J . Appl. Phys.. 50, 2363 (1979). (146) Imshennik, V. K., Suzdalev, I . P., Litterst, F. J., Soc. Phys.-Solidstate

(147) Iwamoto, N., Tsunawaki, Y., Nakagawa, H., Yoshimura, T.. Wakabayashi,

(148) Jach, J., Nabatian, D., Semicond. Insul.. 3, 23 (1977). (149) Jacobs, 1. S., Levinson, L. M., Hart, H. R., Jr., J , Appl. Phys., 49, 1775

(1979).

(Engl. Trans/.), 20. 1985 (1978).

N., J . Non-Cryst. Solids. 29, 347 (1978).

1197R) ~ - ~ .

(150) Jaggi. N. K.. J . Phys. C , 12. L243 (1979). (151) Jaggi, N. K.. Rao. K. R . P. M., NDTInt., 11, 281 (1978) (1521 Jain. R.. Lonaworth. G.. J . Phvs. F. 8. 363 (1978). i 153) Janot, C., "Pr&eedings of the lnternationai Conference on Mossbauer

Spectroscopy, Volume 2", D. Barb, D. Tarina, Ed., Documentation Office, Central Institute of Physics, Bucharest, 1978, p 229.

(154) Johnston, J. H., Glasby, G. P., Geochem. J. , 12, 153 (1978). (155) Jones. W., Thomas, J. M., Thorpe, R. K., Tricker, M. J., Appl. Surf. Sci.,

1, 388 (1978). (156) Jones, C. H. W., Tse, A,, J . Appl. Phys., 49, 4598 (1978). (157) Kagan, Yu., Afanas'ev, A. M.. Kohn, V. G., J , Phys. C, 12, 615 (1979).

ANALYTICAL CHEMISTRY, VOL. 52, NO. 5, APRIL 1980 183R

(158) Kalvius, G. M., Cohen, D., Dunlap, B D., Shenoy, G. K., Phys. Rev. 6 , 18 4581 11978)

\ . - . - I . . , . - - .

(159) Kalyamin, A. V.. Kuvshinov, V. A., Pal'chevskii, V. V., Russ. J. Phys. Chem. Enol. Trans/.). 52. 1693 (1978).

(160) Karnzin,-A. S., Bokov, V. A., SOY. Phys.-Solid State(€ngi. Transl.), 19,

(161) Kapitanov, E. V., Yakovlev, E. N., Phys. Status SolidiA, 53, 473 (1979). (162) Karger, M., Wagner, F. E., Moser, J., Wortmann, G., Iannarella, L.,

Hyperfine Interac., 4, 849 (1978). (163) Karraker, D. G., Stone, J. A., J. Inorg. Nucl. Chem., 39, 2215 (1977). (164) Katila, T. E., Kiuru, E.. Riski, K. J., Sipila, H., Vanha-Honko, V.,

"Proceedings of the International Conference on Mossbauer Spectroscopy, Volume I", D. Barb, D. Tarina, Ed., Documentation Office, Central Institute of Physics, Bucharest, 1977, p 9.

(165) Keisch, E., Gibbon, G. A,, Akhtar, S., Fuel Process. Tech., 1, 269 (1978). (166) Kessler, G. E., Rochev, V. Ya., Romanov, L. M., Kevdin, 0. P. , Polymer

Sci. (Engl. Transl.), 19, 480 (1977). (167) Kim, C. S., Boolchand, P., Phys. Rev. B, 19, 3187 (1979). (168) Kobeissi, M. A.. Chow, L., Hohenemser, C., Hyperfine Interac., 4, 485

(169) Kobeissi, M. A., Hohenemser, C., Rev. Sci. Instrum., 49, 601 (1978). (170) Kopcewicz, B., Kopcewicz, M., Tellus, 30, 562 (1978). (171) Kopcewicz, M., Kotlicki, A., Solid State Commun., 27, 1409 (1978). (172) Kovalenko, P. P., Labushkin, V. G., Sarkisyan, V. A,, Sov. Phys.-JETP

(173) Kucera, J., Kucera, J., Czech. J. Phys. 6, 28, 560 (1978). (174) Kunrath, J. I., Muller, C. S., Frank, E., J. Therm. Anal., 14, 253 (1978). (175) Lagunov, V. A., Polozenko, V. I., Ind. Lab. (Engl. Transi.), 43, 1078

(176) Lang, G., Spartalian, K., Reed, C. A,, Coilman, J. P., J . Chem. Phys.,

(177) Langouche, G., Dezsi, I., van Rossum, M., de Bruyn, J., Coussement,

(178) Langouche, G., Dezsi, I., van Rossurn, M., de Bruyn, J., Coussement,

(179) LaPrice, W. J., Uhrich, D. L., J. Chem. Phys., 71, 1498 (1979). (180) Latorre, R. C., Costamagna, J. A., Frank, E., Abeledo, C. R., Frankei,

(181) Laviile, H.. Bernier, J. C., Sanchez, J. P., Solid State Commun., 27, 259

(182) Lee, R. J., Huggins, F. E., Huffman, G. P., Scanning Nectron Microsc.,

(183) Leidheiser, H., Jr., Nagy-Czako, I., Varsanyi, M. L., Vertes, A,, J. Electrochem. Soc., 128, 204 (1979).

(184) Leidheiser, H.. Jr., Vertes, A., Varsanyi, M. L., Nagy-Czako, I . , J. Nectrochem. SOC., 126, 391 (1979).

(185) Leja, E., Korecki, J., Krop, K., Toil, K., Thin SolidFilms, 59, 147 (1979). (186) Liljequist, D., Bodiund-Ringstrom, B., Nucl. Instrum. Methods, 160, 131

(1979). (187) Liljequist, D., Ekdahl, T., Baverstam, U., Nucl. Instrum. Methods, 155,

529 (1978). (188) Litterst, F. J., Ogrodnik, A., Kalvius, G. M., Hyperfine Znterac.. 4, 879

(1 978). (189) Litterst, F. J.. Ramisch. R., Kalvius, G. M I J. Non-Cryst. Solids. 24, 19

(1977). (190) Litterst, F. J., Schichl, A., Baggio-Saitovitch, E., Micklitz, H., Friedt. J.

M., Ber. Bunsenges. Phys. Chem., 82, 73 (1978). (191) Litterst, F. J., Schichl, A., Kalvius. G. M., Cham. Phys., 28. 89 (1978). (192) Litterst, F. J., Suzdalev. I. P., "Proceedings of the International Con-

ference on Mossbauer Spectroscopy. Volume 2", D. Barb, D. Tarina, Ed., Documentation Office, Central Institute of Physics, Bucharest, 1978, p 197.

(193) Liu, C. M., Ingalls, R., Rev. Sci. Instrum , 49, 1680 (1978). (194) Long, G. J., Alway, D. G., Barnett, K. W., Inorg. Chem., 17, 486 (1978). (195) Long, G. J., Longworth, G., Battle, P., Cheetham, A. K., Thundathil, R.

(196) Longworth, G., Becker, L. W., Thompson, R., Oldfield, F., Dearing, J. A,.

(197) Longworth, G., Jain. R. , J . Phys. F , 8, 351 (1978). (198) Longworth, G., Jain, R., J. Phys. F . 8. 993 (1978). (199) Longworth, G.. Warren, S. E.. J . Archaeol. Sci., 6, 179 (1979) (200) Ludwiczek, H., Preisinger, A., Fischer. A., Hosemann, R., Schonfeld, A,,

(201) Maeda, Y., J. Phys. (Paris), Colloq., 40, C2-514 (1979). (202) Maeda, Y., Kagaku Zokan (Kyoto). 76, 191 (1978). (203) Maetz, J., Butt. N. M., Jex. H., Muilner. M.. Phys. Left. 68A, 87 (1978). (204) Maksimov, Yu. V.. Fursova, A. A., Suzdalev, I . P., Margoiis. L., Kush-

nerev, M. Ya., Bull. Acad. Sci. USSR. Div. Chem. Sci. (Engl. Trans/.), 28. 12 (1979).

(205) Malysheva. T. V., Satarova, L. M. Poiyakova, N. P., Geochern. lnt. (Engl. Transl.), 14(4), 117 (1977).

(206) Manning, P. G.. Ash, L. A., Can. Mineral., 16, 577 (1978). (207) Manning, P. G., Ash, L. A., Can. Mineral., 17, 1 1 1 (1979). (208) Martin, C. J., O'Connor, 0. A.. Acta Crystaibgr., Sec. A,, 34, 500 (1978). (209) Martin, C. J., O'Connor, D. A . , Acta Crystallogr., Sect. A, 34, 505 (1978). (210) Massenet, O., Nuci. Instrum. Methods, 153, 419 (1978). (211) Matsushita, E., Matsubara, T . , Prog. Theor. Phys.. 59, 15 (1978) (212) Meisei, W., "Modern Physics in Chemistry, Volume 1". E. Fluck. V. 1.

(213) Meisel, W., Kesztheiyi, L.. Hyperfine Interact., 3, 413 (1977). (214) Meyer, C. T., Pineri, M. H., J. Polym. Sci: Polymn. Phys. Ed., 16, 569

1187 (1977).

(1978).

Lett. (Engl. Transl.), 28, 552 (1978).

(1977).

69, 5424 (1978).

R., Phys. Status Solidi B , 89, K17 (1978).

R., Phys. Status Solidi B , 93, K107 (1979).

R. B., J . Inorg. Nucl. Chem., 41, 649 (1979).

(1978).

1, 561 (1978).

V., Beveridge, D., Inorg. Chem., 18, 624 (1979).

Rurnmery, T. A,, J. SoilSci., 30, 93 (1979).

Vogel, W., J . Catal., 51, 326 (1978).

Gol'danskii, Ed., Academic Press, London, 1977, p 237.

(1978). \ - - ,

(215) Minai, Y., Takeda, M., Wakita, H., Tominaga, T., Radiochem. Radioanal. Left.. 36. 199 (1978).

(216) Minai, Y., Tominaga, T, Radiochem. Radioanal. Lett., 37, 125 (1979) (217) Mineeva, R. M., Phys. Chem. Mineral., 2, 267 (1978).

184 R ANALYTICAL CHEMISTRY, VOL 52, NO. 5, APRIL 1980

(218) Mitin, A. V., Sov. Phys.-Solid State (Engi. Transi.), 20, 941 (1978). (219) Mkrtchyan. A. R., Arutyunyah, G. A,, Arakelyan, A. R., Gabrielyan. R.

(220) Mkrtchyan, A. R., Kocharyan, L. A., Sov. J. Quantum Nectron. (Engl.

(221) Montano, P. A., Barrett. P. H.. Mickiitz, H., Freeman, A. J., Mallow, J.

(222) Moser, J., Wortmann, G., Bykovetz, N., Kalvius, G. M., J. Magn. Magn.

(223) Mbup, S., Sontheimer. F., Ritter, G., Zimmermann, R., J . Phys. Chem.

(224) Motoyama, I . , Watanabe, M., Sano, H., Chem. Lett., 513 (1978). (225) Mulien, J. G.. Stevenson, J. R., Nucl. Instrum. Methods, 153, 77 (1978). (226) Munck, E., "The Porphyrins, Volume IV", D. Dolphin, Ed., Academic

(227) Mysen, B. O., Virgo, D., Am. J. Sci., 278, 1307 (1978). (228) Nagy, D. L., Appl. Phys., 17, 269 (1978). (229) Nalovic, L., Janot, C., Rev. Phys. Appl., 14, 475 (1979). (230) Nascimento, M. S., Garg, V. K., J . Chem. Phys., 66, 5798 (1977). (231) Niesen, L., Ofer, S., Hyperfine Interact., 4, 347 (1978). (232) Nikolaev, V. I., Belova, V. M., Stefanovich. S. Yu.. Instrum. €xu. Tech.

G., Phys. Status Solidi B. 92, 23 (1979).

Transl.), 7, 898 (1977).

V.. Phys. Rev. B , 17, 6 (1978).

Mater., 12. 77 (1979).

Solids, 39, 123 (1978).

Press, New York, 1979, p 379.

USSR ( fng l . Transl.). 21. 28 (1978).

tosnvi. I. Yu.. Sov. Phvs.-J€TPfEnol. Trans/.\. 47. 337 (1978). (233) Nikolaev, I. N.. Delyagin, N. N., Nesterov, V. I., Potapov, V. P., Bezo-

(234) Gninger, d. C., Jr.. Schr&er, D., 2. Phys.~Ciem.'Solas, 39, i37 (1978). (235) Nolet, D. A., Burns, R. G., Phys. Chem. Miner., 4, 221 (1979). (236) Nylandsted Larsen, A,, Weyer. G.. J. Phys. F , 9, 27 (1979). (237) Ouseph, P. J., Groskreutz, H. E., Johnson, A. A., Meteoritics, 14, 97

(238) Owens, A. H., Chien, C. L., Walker, J. C., J. Phys. (Paris), Collbq., 40,

(239) Papaefthymiou, G. C., Kaufman, K. S., Frankel, R. B., Rosenthal, A,, J . Appi. Phys.. 49, 1815 (1978).

(240) Parish, R. V., "The Organic Chemistry of Iron, Volume l", E. A. Koerner von Gustorf, F. W. Greveis, I . Fischler, Ed., Academic Press, New York, 1978, p 175.

(241) Parish, R. V., Rush, J. D., Chem. Phys. Lett., 63, 37 (1979). (242) Parkin, K. M., Loeffler, B. M.. Burns, R. G., Phys. Chem. Miner., 1, 301

(243) Pasternak, M., Barrett, P. H., Solid State Commun., 27, 771 (1978). (244) Pasternak, M., Shamai. S., Cryogenics, 19, 40 (1979). (245) Pattyn. H., Coussement. R., de Bruyn, J., Odeurs. J.. van Rossum, M..

J. Nucl. Mater., 69 & 70. 764 (1978). (246) Pawlowski, Z . . Cudny, W.. Nucl. Instrum. Methods, 157, 287 (1978). (247) Pearson, D. I. C., Williams, J. M., "Proceedings of the International

Conference on Mossbauer Spectroscopy, Volume l", D. Barb, D. Tarina, Ed., Documentation Office, Central Institute of Physics, Bucharest, 1977, p 103.

(248) Peev, T. M., Dimitrov, P. T., Mitev, T. T., Peneva, L. S., J. Anal. Chem. USSR (Engl. Transl.) 33, 304 (1978).

(249) Peev, T. M., Nagy, S., Vertes, A., Dobrevskii, 1.. Radiochem. Radioanal. Lett.. 39, 47 (1979).

(250) Peregudov, V. N., Hyperfine Interact., 3, 353 (1977). (251) Perlow, G. J., Ed., "AIP Conference Proceedings, No. 38: Workshop

on New Directions in Mossbauer Spectroscopy", American Institute of Physics, New York, 1977, 152 pages.

(252) Periow, G. J., Phys. Rev. Lett., 40, 896 (1978). (253) Pettit, J. W., Levy, R. A., Nucl. Instrum. Methods. 159, 561 (1979). (254) Player, M. A., Woodhams, F. W. D., J. Phys. E , 11, 191 (1978). (255) Pound, R. V., Vetterling, W. T., J. Phys. (Paris), Cobp. 40, C2-3 (1979). (256) Povitskii, V. A., Saluqin, A. N., Baldokhin, Yu. V., Makarov, E. F., Elis-

(1979).

74 (1979).

(1977).

tratov, N. V., Phys. Starus Solidi6. 87, KlOl (1978). (257) Prasada Rao, T. S. R., Menon, P. G., J. Catal. 51, 64 (1978). (258) Raman. T.. Rao, G. N., Chakravorty, D., J . Non-Cryst. Solids. 29, 85

11978). (259) Rao, K. R. P. M., Trans. Indian Inst. Met., 32, 10 (1979). (260) Raupp, G. E., Deigass, W. N., J. Catal. 58, 337 (1979). (261) Raupp, G. B., Delgass, W. N., J. Catal., 58, 348 (1979). (262) Raupp, G. B., Delgass, W. N., J. Catal., 58, 361 (1979). (263) Reintsema. S. R., Drentje, S. A., de Waard, H., Hyperfine Interact., 5,

(264) Reintsema. S. R., Verbiest, E., Cdeurs, J., Pattyn, H., J. Phys. F , 9, 1511

(265) Ritter, G., Konig, E., Irler, W., Goodwin, H. A,, Inorg. Chern., 17, 224

167 (1978).

(1979).

(1978). (266) Rots, M.. Namavar, F. , Langouche, G., Coussement, R , van Rossum.

(267) Roy, S K., Singh, K. M.. Bhattacharya, 0 . L., Indian J . Pure Appl. Phys.. M., Boolchand, P., J. Phys. F , 8, L117 (1978).

16. 1019 11978). (268) Ruebenbauer, K.. Birchall, T.. Hyperfine Interact., 7, 125 (1979). (269) Russell, P. E., Montano, P. A., J . Appl. Phys., 49, 1573 (1978). (270) Sadykov, E. K., Sov. Phys.-Solid State(€ngl. Trans/.), 19, 963 (1977). (271) Sakamoto, I . , Hayashi, N., Furubayashi, 8.. J . Phys. (Paris), Colloq.,

(272) Salomon, D., West, P. J.. Weyer. G.. HyperfineInteract,. 5, 61 (1977). (273) Sarns, J. R.. Tsin. T. 6.. "The Porphyrins, Volume 1V"- D. Dolphin. Ed.,

(274) Sarma, P. R., Sharma, A. K.. Tripathi, K. C., Nucl. Ins t rum Methods,

(275) Sato, H., Tominaga, T., Bull. Chem. SOC. Jpn.. 52, 1402 (1979). (2761 Sawicka, B. D., Drwiesa, M., Sawicki, J. A,, Stanek. J., Hyperfine

40, C2-39 (1979).

Academic Press, New York. 1979, p 425.

164, 591 (1979).

Interact., 5, 147 (1978). 1277) Sawicki, J. A., Stanek, J., Sawicka, B. U., Kowalski, J., "Proceedings

of the International Conference on Mossbauer Soectroscow Volume 1 ". D Barb. D. Tarina. Ed., Documentation Office, Central 1nstii;te of Physics, Bucharest. 1977, p 15

Anal. Chem. 1980, 52, 185R-199R

(278) Sedunov, V. K., Men'shikova, T. Ya., Mitrofanov, K. P., Reiman, S. I . , Rokhlov, N. I., Met. Sci. Heat Treat. (Engl. Transl.), 19, 742 (1977).

(279) Sekhon, S. S., Kamal, R . , J . Appl. Phys.. 49, 3444 (1978). (280) Seregin, P. P., Nasredinov, F. S., Bakhtiyarov, A. Sh., Phys. Status Solidi

(281) Seregin, P. P., Nasredinov, F. S., Vasil'ev, L. N., Phys. Status Solidi A .

(282) Shechter. H., Suzzanne, J., Dash, J. D., JPhys. (Paris), 40, 467 (1979). (283) Shenoy, G. K., Wagner, F. E.. Ed., "Mossbauer Isomer Shifts", North-

Holland Publishing Co., Amsterdam, 1978, 956 pages. (284) Shibuya, M., Endo, K., Sano, H., Bull. Chem. Soc. Jpn., 51, 1363 (1978). (285) Simmons, G. W., Leidheiser, H., Jr., "Characterization of Metal and

Polymer Surfaces: Volume 1, Metal Surfaces", L.-H. Lee, Ed., Academic Press, New York, 1977, p 49.

(286) Singh, A. K., Jain, B. K., Chandra, K., J . Phys. D , 11, 55 (1978). (287) Sitek, J., Kruziiak. J., Tomasich, M., Cirak, J., Prejsa, M., Phys. Status

SoiidiA, 47, 287 (1978). (288) Smith, G. V., Liu, J. H., Saporoschenko, M., Shiley, R., fuel, 57, 41

(289) Sokol'skii, D. V., Aiekseeva, G. K., Khlystov. A. S.. Ashkevich, V. I., Kotova, G. N., React. Kinet. Catal. Lett., 6, 59 (1977).

(290) Solomon, H. D., Levinson, L. M., Acta Metall., 26, 429 (1978). (291) Soltwisch, M., Elwenspoek, M., Quitmann, D., AIP Conference Pro-

ceedings, No. 38: Workshop on New Directions in Mossbauer Spectroscopy", G. J. Perlow, Ed.. American Institute of Physics, New York, 1977, p 114.

(292) SDencer. C. D.. Smith. P. A.. Stillwell. R. P.. J. Phvs. Chem. Solids. 39,

B , 91, 35 (1979).

45, 11 (1978).

(1978).

' 103 i1978). (293) Spiering, H., Nucl. Instrum. Methods, 154, 295 (1978). (294) Spiering, H., Hosl, S., Vogel, H., Phys. Status Solidi 8 , 85, 87 (1978). (295) SDierina. H.. Witzaall. R.. Hvoerfine Interact.. 5. 265 11978). (296j Siadnik:'Z. M.. M;ssbauer€ff. Ref. Data J. , 1, 217 (1978). (297) Stevens, J. G., Bowen, L. H., Anal. Chem., 50, 176R (1978). (298) Stevens, J. G.. Trooster, J. M., J . Chem. Soc., Daiton Trans., 740

(299) Stiller, A. H., McCormick, B. J., Russell, P. E., Montano. P. A,, J . Am.

(300) Stiller. A. H., Renton, J. J., Montano, P. A,, Russell, P. E., fuel, 57, 447

(301) Syn, C. K., Fub, B., Morris, J. W., Jr., Metall. Trans. A, 9A, 1635 (1978). (302) Syono, Y., Ito, A., Horie, O., J. Phys. SOC. Jpn.. 46, 793 (1979). (303) Takeda, Y., Naka, S.. Takano, M., Shinjo, T., Takada, T., Shimada, M.,

(304) Taragin, M. F., Nucl. Instrum. Methods., 150, 607 (1978). (305) Teiilet, J., Job, D., Varret, F.. Chappert, J., Nucl. Instrum. Methods, 155,

(306) TenutaAzevedo, A. L.. da Silva, E., Scr. Metall., 12, 113 (1978). (307) Tewari, S. P., Swaminathan, K.. Solid State Commun., 24, 65 (1977). (308) Tominaga, T., Sato, H., Radiochem. Radioanal Lett., 33, 53 (1978). (309) Tominaga, T., Takeda, M., Mabuchi, H.. Emoto, Y., Archaeometry, 20,

(310) Townsend, M. G., Webster, A. H., Horwood. J. L., Roux-Buisson. H., J .

(311) Trammell, G. T., Hannon, J. P., Phys. Rev. B , 18, 165 (1978). (312) Tricker, M. J., J . Mater. Sci., 14, 995 (1979). (313) Tricker, M. J., Ash, L. A., Jones, W., Surf. Sci., 79, L333 (1979).

(1979).

Chem. Soc., 100, 2553 (1978).

(1978).

Mater. Res. Bull., 13, 61 (1978).

97 (1978).

135 (1978).

Phys. Chem. Solids, 40, 183 (1979).

(314) Tripathi, K. C., Sarma, P. R., Gupta, H. M., J . Polym. Sci: Polym. Lett.

(315) Trooster, J. M., de Valk, W., Hyperfine Interact., 4, 457 (1978). (316) Tsankov, L., Bonchev, Ts., Bulg. J. Phys., 5, 149 (1978). (317) Tseng, P. K., Chuang, S. Y., Chen, H. S.. J . Appl. Phys., 50, 4292

(1979). (318) Uehara, S., Maeda, Y., "Proceedings of the International Conference

on Mossbauer Spectroscopy, Volume l", D. Barb, D. 'Tarina, Ed., Docu- mentation Office. Central Institute of Physics, Bucharest, p 17.

(319) Uehara, S., Maeda, Y., Annu. Rep. Res. React. Inst., Kyoto Univ., 11,

(320) Unknown Editors, J . Phys. (Paris), Colloq. C2, 40 (1979), 704 pages. van Diepen, A. M., Popma, T. J. A., Solid State Commun., 27, 121

(322) van Diepen, A. M., Vledder, H. J., Langereis, C.. Appl. Phys., 15, 163 (1978).

(323) van Rossum, M., de Bruyn, J., Dezsi, I., Langouche. G., Coussement, R.. Phys. Status SolidiA, 52, K31 (1979).

(324) van Rossum, M., de Bruyn, J., Langouche, G., de Potter, M., Coussement, R., Phys. Lett. A , 73, 127 (1979).

(325) Varret, F., Naudin. F., Rev. Phys. Appl., 14, 613 (1979). (326) Vdovykhin, G. P., Grachev, V. I., Malysheva. T. V., Geochem. Int. (Engl.

Transl.), 14(3), 119 (1977). (327) Vereshchak, M. F., Zhetbaev, A. K., Ibragimov, Sh. Sh., Phys. Status

SolidiA, 52, 415 (1979). (328) Vertes, A., Leidheiser, H., Jr., Varsanyi. M. L., Simmons, G. W., Kiss,

L., J . Electrochem. Soc.. 125, 1946 (1978). (329) Viegers, M. P. A. Trooster, J. M., "AIP Conference Proceedings, No. 38:

Workshop on New Directions in Mossbauer Spectroscopy", G. J. Perlow, Ed., American Institute of Physics, New York, 1977, p 102.

(330) Viegers, M. P. A., Trooster, J. M., Bouten, P. C P., Peters-Rit, T., J . Chem. Soc., Dalton Trans.. 2074 (1977).

(331) Vincze, I . , Solid State Commun., 25, 689 (1978). (332) Vincze, I . , Babic, E., Solid State Commun., 27, 1425 (1978). (333) Vollenbroek, F. A., Bouten, P. C. P., Trooster, J. M., van den Berg, J.

P., Bour, J. J., Inorg. Chem., 17, 1345 (1978). (334) Von Eynatten, G., Bommel, H. E., Appl. Phys., 14, 415 (1977). (335) Wagner, F. E., Wortmann, G.. "Hydrogen in Metals I . Basic Properties".

G. Alefeld, J. Volkl, Ed., Springer-Verlag, Berlin, 1978, p 131. (336) Wang, G. W., Chirovsky. L. M., Lee, W. P., Becker, A. J., Groves, J. L..

Nucl. Instrum. Methods, 155, 273 (1978). (337) Weiss, H., Langhoff, H., Z. Phys. B , 33, 365 (1979). (338) Wenzel, H., Sherif, A. Kh. Opalenko, A. A., Kuz'min, R. N., Insfrum. Exp.

Tech. USSR(€ngl. Trans/.), 20, 262 (1977). (339) Wickberg, J. N., Eck, J. S., Radiat. Eff., 38, 83 (1978). (340) Williamson, D. L., Dale, J. H., Josephson, W. D., Roberts, L. D., Phys.

Rev. B , 17, 1015 (1978). (341) Williamson. D. L., Schupmann. R. G., Materkowski. J. P., Krauss, G.,

Mefall. Trans. A , 10, 379 (1979). (342) Wit, H. P., Niesen, L., de Waard, H., Hyperfine Interact., 5, 233 (1978). (343) Wong, H., Sedney, D., Reiff, W. M., Frankel, R. B., Meyer. T. J., Salmon,

D., Inorg. Chem.. 17, 194 (1978). (344) Yarmarkin. V. K.. Teslenko. S. P.. Knvazev. A, I.. Phvs. Status Solid;

Ed., 16, 629 (1978).

189 (1978).

(32;1)978).

' A, 45, 63 (1978). (345) Zimmermann, R . , Konig, J . Phys. Chem. Solids, 38, 779 (1977). (346) Zolotoyabko, E. V., Kashcheev, V. N., J . Phys. C , 10, 4599 (1977).

Enzymes in Analytical Chemistry

Myer M. Fishman

Department of Chemistry, The City College of the City University of New York, New York, New York 10031

Over the years, there has been a steady growth in the use of enzymes as analytical tools in the industrial, medical, pharmaceutical, clinical, and food fields. The literature has become rather extensive and continues to grow each year. Much of the recent literature has been periodically reviewed in this Journal (I&$), and the last such review covered the period January 1976 through December 1977. This one now attempts to cover the period .January 1978 through December 1979. However, out of sheer necessity, because the literature has become so voluminous, not all that has appeared in print has found its wag' into this article. Each time a review has been written, there usually appear special monographs, reports on symposia, etc.. and this continues to be a rich source of information for those who are interested in establishing a new

Myer M. Fishman is Professor of Cheniistry and Chairman of the Biochemistry Division of the Chemistry Department at the City College of the City University of New York. He re- ceived his B.S. degree in Chemistry from the City College and the M.S. and PhD. degrees from the University of Minnesota. His re- search interests have included the use of dextran as a plasma expander, intravenous infusion of fat emulsions. carcinogenesis of plastics, and the interaction of macromole- cules with antibiotics and dyes. He is a member of the ACS. Sigma Xi, the American Association for Cancer Research, and the American Society of Biological Chemists.

base (6-21). For many reasons, enzymes were being used on an in-

creasing scale. Characterized as being both specific and sensitive, yet easy t o use and reproducible. enzymes were

shown to be rather unique but powerful catalysts. However, there were serious limitations to their use on any regular basis.

0003-2700/80/0352- 185R$01 .OO/O 1980 American Chemical Society 185 R