Infrared spectrometry - Analytical Chemistry (ACS Publications)

Anal. Chem. , 1972, 44 (5), pp 241–250. DOI: 10.1021/ac60313a025. Publication Date: April 1972. ACS Legacy Archive. Cite this:Anal. Chem. 44, 5, 241...
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(982) Wallace, H. F., Hayes, K. E., J . Cutul., 18, 77 (1970). (983) W d e , T., A& p h m . szleciecr, 5 , 367 (1968). (9%) Warren. B. C. H., Ddzell, M. G., . “GBBchroinatography in Biology and Medicine,” R. Porter, Ed., J. & A. ChiirchiLl --- -- Ltrl.. ---,London. 1969. DD 59-82. (985) Warren, B. C. H., ‘+ve[o& J . E., “GT Chr,ynatography m Biology and Medmne, R. Porter, Ed., J. & A. Churchill Ltd., London, 1969, p 65-9. (986) Wssik, S. P., Tsang, ANN,. CHEM.,42, 1648 (1970). (987) Watson, J. T., “Ancillary Techniques of Gas Chromatogra hy,” L. S. Ettre and W. H. McFadSen, Ed., Wilev-Interscience. New York, N.Y., ( 9 g y $ p 145-225. . atta, R. R., 3. Ass. mc. Anal. Chem. 53, 787 (1970). (989) deems,G. W., Hoffman, C.. A., Howard, A. R., J . Chromatogr. Sa.,9 , 444 (1971). (990) Weinreich, P., Chro.omatog.aphia, 3, riS0 (1971). (991) Weiss,’ G. H., Separ. Sn’., 5 , 51 (1970). (992) Wernbera, O., Lamm, C. G., ‘ Nielsen, T.,-‘J. Chromato&. Sci., 9, 373 (1971). 1993) Wicar. S.. Novak., J.., J . Chromatoor.. 53; 429 (i9iO). (994) Wicar, S., Novak, J., Ruseve Rekshieva, N., ANAL.CHEM.,43, 1945 (1971). (995) Wicarova, O., Novak, J., Janak, J., J . Chrotnatour.. 51. 3 (1970). (996) Wilson,”W. O:,Price, J. G. W., 3. Chromatogr. Sci., 8, 31 (1970). (997) Windham, E. S., J . Ass. OJic. Anal. Chem.,. 52, 1237 (1969). (998) Wmdlev. W. T.. British Patent ‘ 1.173.059 (Dec. 3. 1969). (999) Winfrey, J. 6, Bethel, C. E., Jr., J . Chromatogr. Sci., 9, 353 (1971). (1OOO) Winnett, G., ibid., 8, 554 (1970).

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(1001) Winski, D. T., Rubel, M., Drug Comet. Znd. 106 j5), 48, 156 (1970). (1002) WOM, 6. J., h v y , R. J., W&er, J. Q., Ind. Res.,13 ( l ) , 40 (1971). (1003) Wolf, F. J., “Separation Methods in -0yanic Chemistiy and Biochemist Academic Press, New York, N!.?!. 1969. (1604) ‘WOtG, H. J., Clark, S. J., “Methods of Biochemical Analysis,” Vol. 18, D. Ghck, Ed., Interscience, New York, N.Y., 1970, pp 339-72. (1005) Wu. F. F. H., G t z , J., Jamieson, W. D., Messon, C. R., J . Chronzatogr., 48, 515 (1970). (1006) Wurst, M., Collect. Czech. Chem. Commun., 34, 3297 (1969). (1007) Yanovskii. S. M., Tr. Vses. . Na;rchn.-18sledd.. Gwl. Neft. Znstd., 64, 121 (1970). (1008) Bid., p 134. (1009) Yanovskii, S. M., Alksnis, 0. N., Lieberman, I. I., Sazonov, M. L., Zhukhovitskii, A. A., Zwod. Lab., 36, 136 (1970). 11010) Yanovskii. S. M.. Zhukhovitskii. ‘ A. A. Zh.Fiz. Khim., &,-1625 (1970).’ (1011) kavoiskii, A. V., Zhukhovitskii, A. A., Grigoryan, V. A., Zavod. Lab., 35, 1031 (1969). . (1012) Yip, G., J . Ass. OJic. Anal. Chem., 53. 358 11970). (1013) Young, C. L., J . Chromatogr. Sci., 8, 103 (1970). (1014) Young, R. W., J . Agr. Food Chem., 18, 164 (1970). (1015) Zado, F. M., Fabecic, J., J . Chrotnatom.. 51. 37 (1970). (1016) Zad;, F. M., Fabecic’, J., Zemva, B., Slivnik, J., “Column Chromatography,” E. sz. Kovats, Ed., Swiss Chemists’ h o c . , 1970, p 227-9. (1017) Zakupra, V. A., Dogrov, V. S., Grona. L. Ya.. Lizocub. A. P.. Khim. Tekhn&-Topl.’Mdseg 15, 56 (1970). (1018) Zalkin, V. S., Zuuod. Lab., 36, 129 (1970).

(1019) Zelvenskii, V. Yu., Sakodynskii, K. I., Genel, S. A., Neftekhimiya, 10, 135 (1970). (1020) Zhukhovitskii, A. A., Sazonov, M. L., J . Chromcrtoor.. 49. 153 ~ - 11970). (1021) Zhukovitskii, i. ’A., Sasonov, M: L., Lunskii, M. K., Yusfin, V., ibid., 58, I

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(1022) Zielinski, E., Chem. Anal. (Warm ~ ) 14, , 521 (1969). (1023) Zikanova, A., J . Chromatogr. Sd, 9, 248 (1971). (1024) Zizin, V. G., Berdina, L. Kh., Avdeyeva, M. P., Zwod. Lab., 36, 1307 (1970). (1025) Zlatki, A., Ed., “Advances in Chromatography, 1970,” University of Houston Publishers, Houston, Texas, 1970. (1026) Zlatkis, A., Ed .,,, “Advances in Chromatography 1971, University of Houston Publishers, Houston, Texas, 1971. (1027) Zlatkis, A., Kaufman, H. R., Durbin, D. E., J . Chroniatogr. Sci., 8, 416 (1970). (1028) Zlatkis, A., Pettit, B. C., Chromatographia, 2 , 484 (1969). (1029) Zlatkis, A., Pretorius, V., Ed., “Preparative Gas Chromatogra h Wiley-Interscience, New York, 1971. (1030) Zorin, A. D., Frolov, I. A., Karabanov, N. T., Kedyarkin, V. M., Balabanov. V. V., Kusnetsova, T. S.. Gurianov, .A. N., Zh. Anal. K h k , 25; 389 (1970). (1031) Zumwalt, R. W., Kuo, K., Gehrke, C. W., J . Chromatogr., 57, 193 (1971). (1032) Zuyeva, G. Ya., Lukyankova, V. V., Ponomarenko, V. A., Zzv. Akad. Nauk SSSR, Sm. Khim., 1971, 646. (1033) Zvarova, T. S., Zvara, I., J . Chromatogr., 44, 604 (1969). (1034) Ibid., 49, 290 (1970).

5.9:;

Infrared Spectrometry Robert S. McDonald, General Electric Corporate Research and Development Center, Schenectady, N. Y . I2301

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covers the same twoyear period as Chemical Abstracts (CA) volumes 72-75 (1970-71). Selection of References. For the most part, the initial selection of referencea was based on a computer search of HIS REVIEW

Chemical Abstracts Crmdensates (CAC). Concurrently with the preparation of this review, the author has been developing an interactive computer program called LISE (LIterature Search and Edit). LISE is designed to assist an author in compiling and editing references. The basic objective in the design of LISE has been to maintain the bibliography in computer readable form while a user organizes his references. The ultimate aim is to have the computer type out the bibliography in a form acceptable to a journal,

As is often the case with a new computer program, LISE has interfered with preparation of this review as much as it has helped. LISE, itself, has benefited greatly by direct involvement with the practical problems of the review. The bibliography was actually typed by computer directly from the CAC data base with only minor corrections. The latter were carried out with an interactive text editor. I n addition to getting LISE to work, i t has been necessary to develop procedures for its use. Only now is a n effective procedure beginning to evolve, too late for its impact to be felt in this review. The logical unit of CAC is a condensate. Each condensate corresponds to a n abstract in CA, and contains the C A

reference, title, authors’ names, location, journal reference, and a set of keyword phrases designed for computer searching. The keyword phrases together with the title amount to a highly abbreviated abstract. Computer listings of the condensates have played a large part in the selection of articles for this review. The edition of CAC on 7 track magnetic tape was used. This data base makes use of a limited set of about 50 graphic characters (upper case letters only). It was necessary for LISE to translate back to capitals and lower case for the journal. A search consists of a character-bycharacter comparison of both title and keyword phrases to a set of term which make up a projile. A term is a phrase,

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word, or fragment of a word. The terms which comprise a profile are combined by means of the logical operations: OT, and, not, which determine whether the terms must be present, absent, or present in certain combinations. A term may be truncated on either or both sides, or not a t all. The symbol used in CAC profiles to indicate truncation is the asterisk (*) . If one side of a term is truncated, any character is acceptable adjacent to that side of the term; otherwise, only blank or punctuation is acceptable. The term phenyl*, for example, which is truncated on the right, matches phenylene, as does *phenyl*, which is truncated on both sides. The terms *phenyl and phenyl do not match

phenylene. A search is carried out by checking each letter in the text to see if any term in the profile starts with that letter. If so, matching of the term is continued character-by-character until the end of the term, or text, or until the characters do not match. If the end of the term comes first, that term is a hit term. After a complete condensate has been scanned, the combination of the hit terms is evaluated using the UT, and, or not connectives as specified in the profile. If the result of this evaluation is true, the condensate is consideredto be a hit. For this review, an initial search of CAC was carried out using the terms: infrared,infra-red,infra red, or ir. Over 6500 hits were obtained, approximately 1% of the number of papers covered by CA for the two-year period. This profile obviously was not broad enough to isolate all articles of interest to an analytical infrared spectrometrist. For example, vibrational spectrometry, molecular vibrations, and various terms related to apparatus might have been included. However, it is judged that this would have produced so many hits that it would have been impossible for the author (not the computer) to process them in time for the review. Thus, the decision was made to carry on with 6500 hits, which contained a very large proportion of articles of interest (>95’%). The only topic outside of infrared spectrometry which received a significant number of hits was iridium (CAC uses ir as a keyword for both infrared and iridium). Some of the hits due to iridium were on the infrared spectrometry of iridium compounds, so it was impractical for the search program to ignore items containing iridium. A few false hits were due to such items as IR100, etc. At this stage, the complete condensate for each hit was printed, and, in addition, each condensate was copied onto another magnetic tape. This gave a new data base of about the same size as one issue of CAC. This data base was searched numerous times for special topics. 242R

The complete listing of condensates was scanned for terms to be used in subsequent searches. The profiles and results of some of these searches are shown in the last part of the bibliography. At this point, all of the false hits would normally have been eliminated by hand. This is not quite as simple with the computer data base as with a card file, and for lack of time it was not done. Several points were clearly evident from examination of the printed data base : 1. It is considerably easier to scan a computer listing and make notes on the listing than it is to scan a card file. 2. It is quite convenient to scan the actual abstracts in the printed edition of CA with the help of a listing in which the condensates appear in order of the CA citation. 3. The key words used by CAC are mostly well chosen, but they do not define the content of a paper in a special field closely enough for the purpose of a review such as the present one. It is essential that a reviewer set up his own keywords to classify the condensates. LISE is designed to permit this to be done, but, again, the time was too short. The total amount of time required to do this is not great, but it needs to be done progressively as the papers appear. 4. There are a number of errors and omissions in the CAC data base used by the author. The most serious of these is that the journal citations are not recorded in the precise form required by a journal. Quite a few (0.05-1%) of the references are missing. Also, the number of typing or key punch errors seems quite large. The effect of a spelling error can be tolerated if it produces a false hit, but not if it causes an important item to be missed. It is not too surprising that there are such errors and omissions, in view of the speed with which CAC is assembled. However, if the data base is to be used for the purpose envisioned here, provision will have to be made for subsequently making the required corrections. The ability of the computer to select items out of the original data base according to various criteria expressed in a profile can be an important contribution to the work of a reviewer. However, in this reviewer’s opinion, it is just as important that the computer produce complete readable listings a t various stages and, finally, that it produce the actual manuscript of the bibliography. Presentation of the Bibliography. The bibliography is divided into four parts: Books, Reviews, Papers of Special Interest, and Selected Topics. For the first three items, the titles are listed in full in the bibliography. The references are arranged in order of the CA citations. This places them in roughly chronological order. The main reason for this ordering is to make it

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easy for the reader to scan the abstracts in CA. Normally, a review contains a number of so-called “critical” remarks which appear in the text, disjoint from the references. This reviewer finds that this makes for difficult reading, and unless there is something very special to be said about a given paper, he would rather read the title. It seems reasonable to him to include the title as part of the reference, and to dispense with comments which do not enlarge upon the title. The required amount of space is about the same. Thus, in a sense, titles which appear in the bibliography are part of this text, and the reader will have to scan them to get the full message of this review. Relatively little selection has been carried out on the Books and Reviews because this reviewer feels that inclusion of items of peripheral interest is desirable. The scope of the activity of many analytical infrared spectrometrists is very broad, and this reviewer does not consider himself qualified to anticipate what might be of no interest to them. He would rather make the scope too broad than too narrow. References to obscure journals and unfamiliar languages are included because they are indicators of good work being done out-side the USA. The languages would have been specified in the references if they had been given in the CAC data base. The papers in the third category have been chosen to give a cross section of topics which the reviewer thinks are of interest to analytical infrared spectrometrists, and topics which he expects to play a role in the development of infrared spectrometry. The last category in the bibliography is intended to give a fairly complete list ing of references in each of a few selected areas, The listings are the results of sub-searches performed on the infrared portion of the data base. The profiles are given, together with the number of hits, the number of false hits, and in some cases, troublesome terms are given. False hits have been deleted. The references themselves consist of a n ordered list of CA citations. This is by far the most compact way to cite an article, and in the reviewer’s opinion, the list is no more illegible than a list of journal citations. I t is far easier to scan a broad selection of the abstracts than to look up a similar number of journal references. The reviewer expects that a reader who has a special interest in one of the fields may take the list to the library and scan through CA for this particular subject. Oddly, it seems more convenient to scan a long list than a short one because of the number of references which one finds in each bound volume of CA. This last section of the bibliography is to be regarded as experimental. Since

the acceptability of this type of presentation is not known, only a small part of the searches are included. Searches have been carried out additionally on polymers (400), minerals (226) , matrix isolation (115), lignin and humic acid (55), lasers (132), detectors (44),farinfrared (419) , hydrogen bonding (286) , carbonyl (225) , and complexes (962). Numbers in parentheses indicate the number of hits. The results of these searches in the abbreviated format will be supplied on request by the reviewer. GENERAL TRENDS IN INFRARED SPECTROMETRY

During the past decade, there has been steady encroachment on the ground which the analytical infrared spectrometrist once dominated. Gas chromatography, mass spectrometry, and N M R have each taken over work once done by infrared spectrometry. Now, LaserRaman spectrometry is moving in. I t seems to have special advantages in the preparation of samples, since the shape of the sample is not nearly so critical as in the case of infrared. The capability of measuring a spectrum of a tiny sample enclosed in a capillary tube seems very attractive. This is going to guarantee that the Raman spectrum will be measured before the infrared spectrum in most cases. Raman spectrometry is so closely related to infrared spectrometry that it seems to be a logical area for the infrared spectrometrist to expand into. The complementary aspects of the two techniques are probably best exploited by a spectrometrist who is active in both fields. Interpretation of infrared and Raman spectra is more of an art than interpretation of NMR and mass spectra. The organic chemist who interprets his own spectra is considerably more a t home with the latter because their results are easily expressed in terms which are directly related to concepts which he is used to. The relationship between vibration frequency and structure is so complex that it requires a specialist to extract all of the information from a n infrared spectrum, and he must make use of subjective factors which have been developed by examining many spectra of known compounds. With the increase in self-service infrared spectrometry, the specialist sees fewer of the day-to-day problems which formerly kept him in training. Only the more difficult problems reach him. Often the needed reference spectra have been measured on a self-service instrument, and he may know nothing about them. There is no question that selfservice has interfered seriously with development of the spectrometrist’s reference files. This is a trend which needs to be reversed. The most drastic way of solving this problem is to prevent the organic chem-

ist from measuring his own spectra. This is not really a satisfactory solution because the quick turnaround of selfservice infrared spectrometry offers important advantages, not only in saving money, but in helping the organic chemist maintain his momentum on a given project. Another way to reverse this trend is to provide better turnaround for spectra which are measured and interpreted by the specialist, so that the organic chemist will not need to do-it-himself on possibly inferior equipment, and possibly with inferior sample preparation. Freedom from paper work is another attractive aspect of do-it-yourself spectrometry. Yet, records have to be kept. Computer management of records for analytical service has not been successful in many labs, partly because of failure to count the enormous cost of delays entailed in holding up analyses while paper work is done. I t will be interesting to see if the integral computer-rapid scan spectrometer system can make use of the computer to cut down on the paper work, and even on the drudgery of maintaining a file of reference spectra. Computer Searching of Infrared Data Files. Considerable activity continues in the field of searching of infrared data files for spectra which match those of an unknown compound. A number of commercial firms offer service in this area. Most searches make use of the ASTM infrared data base (B1, B40, B4l) which is based on the encoding of over 100,000 spectra, each on a single binary Hollerith punched card (960 bits for spectrum, structural data, and identification). Some of the successful programs use only a sub-set of the ASTM data base. The success of these programs is remarkable, considering the brevity of the data on each spectrum. One important feature of these programs is that they do quickly what they can do, and one learns immediately whether or not the search can do anything for him. There has been a tendency to employ the search as a last resort. I n this reviewer’s opinion, the search should be so readily available, and so cheap that it is the first step taken after the spectrometrist discovers that he cannot identify a spectrum by inspection. All commercial searches which this reviewer knows about make use of a sequential search of all pertinent bits in the data base. One way of speeding things up is to search only part of the data base. This old technique was used with the ASTM card file, which soon became too big to pass completely through a card-sorting machine. With computer processing, different approaches for dividing the data base are possible. The data can be encoded so that each spectrum occupies a well defined volume in multidimensional space,

for example. The learning muchine (S9)is one aspect of this approach. A haph coding scheme may be used to define a location in computer memory or bulk storage where the identification may be found. This method requires a means for resolving cases in which two or more spectra compete for the same location. It has been used extensively for managing bulk storage devices in computer systems. The unfortunate aspect of these approaches is that a single error in either the unknown or reference spectrum may throw the search off completely. This reviewer does not feel comfortable about any approach which encodes the data, unless it is to be applied to a finite set of known data. The search can also be speeded up by inverting the data base (850);this is analogous to the peek-a-boo type cards, in which each card corresponds to a particular absorption band or functional group, and each point on the card corresponds to a given compound. This can be carried out in a computer memory. There are serious problems in allowing for the possibility that a given band may be specified in error, but one only uses as much of the data as necessary. This technique offers an approach to another problem of the infrared spectrometrist. This is the problem of how to find the spectra of all of the compounds which have functional groups corresponding to those suspected of being present in a n unknown. Many of the search programs provide as output the serial number of the compound in the ASTM data base. This is highly unsatisfactory. The utility of these programs can be increased enormously by eliminating duplicate hits, and printing the names of the hit compounds. Computer Correlation of Structure with Spectra. Some interesting work is being done on a program which uses a set of objective rules to differentiate between various possible structures on the basis of infrared and mass spectra (S28). This reviewer doubts that such a program will compete with the spectrometrist in the interpretation of spectra. The value of this approach is in establishing the objectivity of the rules by which spectra are classified and interpreted. Fourier Spectrometry. B y now, it is well known that a commercial Fourier spectrometer rivals the performance of the best grating spectrometers (S7). The designers of this instrument have surmounted some very difficult engineering problems having to do with linearity of the detecting system, and precise motion of the moving part of the interferometer, and they are to be congratulated. So far, this reviewer has not seen a satisfactory discussion which reconciles the basic differences of the two instruments.

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If one accepta the Fourier spectrometrist’s claim of an advantage of a factor of 20 to 50 in energy transmission, and another factor of 40 to 50 for the Fellgett or multiplexing advantage, he might expect to see a factor of 800 to 2500 difference in some aspect of the performance. This reviewer would like to know whether the failure to observe this difference is due to the difficulty of achieving theoretical performance with a Fourier spectrometer, or whether the analysis is in error. The process of transforming the data from time space to frequency space confuses the average spectrometrist. It also scrambles the errors. While it may make no sense to the Fourier spectrometrist to talk about scattered light, or distortion due to finite scan speed, there must also be errors of the Fourier spectrometer which have no counterpart for the grating spectrometer. One point which confuses the grating spectrometrist is that he cannot judge the noise in a Fourier spectrogram by looking a t the irregularities in the spectrum. The Fourier spectrometer always operates in a mode that the grating spectrometrist avoids a t all costsnamely, with the apparent noise width precisely equal to the spectral slit width. Problems associated with accurate measurement of Fourier spectra have been discussed recently (849). The effect of seemingly small errors has a rather profound iduence on the resulting spectrum. With the Fourier spectrometer-computer combination, the spectrum is in a computer accessible memory, even before it is plotted out. This should have an important effect on quantitative multicomponent analysis. It may not even be necessary to plot out the spectrum since concentrations can be determined from the spectrum in memory. Of course, the output of a conventional spectrometer can be stored in a computer memory as it is measured, with about the same end result. However, it may be easier to sell the novelty of the Fourier spectrometer which requires the computer than it is to sell a computer to go with a conventional spectrometer. Catalogs of Spectra. Few infrared spectrometrists could function without a catalog of known spectra. The greater the number of reference spectra, the better, provided that particular spectra can be located readily. A number of new catalogs have been published during the period of this review (B6,B12, B13, B26, B e , Rd4, R132, S16, 842, SG), and the ASTM infrared indices have been extended ( B l , B401 B41). Useful groups of spectra appear in other papers too numerous to mention. The commercial collections of spectra and that of the 244R

Coblentz Society continue to grow at a n expensive rate. The Coblents Society has started distribution of higher grade

Evaluated Spectra. Among the new catalogs of spectra, the one by Charles Pouchert of Aldrich Chemical Co. is especially notable because of its size, relatively low cost, and the way in which the spectra are,organized according to chemical classes (BM) Many spectra are grouped on each page. While this makes for some eye strain, it also promotes browsing, which is a real chore when the spectra are on cards, or printed one or two to a page. Unfortunately, not all of the spectra have the same abscissa scale because they were not measured with the same spectrometer. This interferes with the pattern recognition procesg, especially when the spectra are so small. No analytical spectrometrist should be without this book. It is to be hoped that other suppliers of fine chemicals will follow the lead of Aldrich in publishing reference spectra of their products. Because reference spectra are so important, a computer search waa carried out on a profile containing the terms: catalog and collection. This search was a complete failure. (The reader is invited to look over the titles of any catalogs of reference spectra which are handy and choose a profile which will selectively pick out the catalogs without producing too many false hits.) This points up a problem which will become increasingly important aa computer searching becomes more prevalent. The search can only be as good as the title, or the keywords supplied by the abstractor. By far the best way to guarantee that a computer search will select a paper is to make sure that it has the right keywords in the title, and this is under the control of the author. Authors can also help themselves out by careful wording of abstracts. The use of complex combinations of search terms to select a particular topic is not satisfactory. Perhaps some sort of agreement or standardization on descriptors for particular topics is feasible. It may be desirable to permit authors to supply keywords as they now supply abstracts. Lasers. Ever since the laser was first invented, there has been the hope of a narrow line source which could be continuously tuned through a reasonable portion of the spectrum. Such a source could revolutionize infrared spectrometry. Another closely related hope is for a coherent infrared detector. This can work only with a coherent, monochromatic source. This sort of combination is one of the reasons why microwave spectrometry is so elegant. Progress is slow, but encouraging ( S l l , Sd7, S31, S43, R80). The Pbl-,Sn,Te diode laser (811) seems especially inter-

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esting. While the free spectral range is rather small (50 GHs, or 1.5 cm-I), the center wavelength can be set at any point between 6.5 and 28 microns when the laser is manufactured. These lasers should be useful in special applications in gas monitoring where one might sweep the laser back and forth over a single rotational line of a gas. Selectivity and sensitivity should be excellent, provided that the stability is sufficient. A laser technique for measuring ultra low concentrations of gas has been described (836). This method makes use of the change in pressure when the gas is heated by absorption of laser radiation by a rotational line of a gas. This technique is claimed to have measured a concentration of 0.01 ppm of methane in nitrogen using a 15-mW He-Ne laser operating a t 3.39 microns. Several orders of magnitude higher sensitivity are claimed to be feasible. Another new laser technique has been described (S46, 846, $48) in which the infrared emission of a number of vapors has been excited by a COZ laser. This does not seem to be a very sensitive technique, since it was necessary to use wide open slits in the commercial infrared spectrometer with which the fluorescence was measured. Pollution. The above mentioned ultra high sensitivity laser technique (S36) should have applications in the measurement of atmospheric pollution. I n another interesting application, more conventional techniques are being used to identify harmful minerals in mine dusts (Sd4-Sd6). It is understood by the reviewer that these techniques may be applied on a rather large scale for monitoring the daily exposure of miners to dusts which cause silicosis. Infrared Detectors. I n spite of all the advances in infrared detectors, there has not been a noticeable change in the sensitivity of detectors for commercial double beam infrared spectrophotometers. This is largely because the user of such a spectrophotometer, insists on covering a very broad region of the spectrum, and because it is just too much trouble to maintain a cryogenic detector in a routine service operation. However, for special regions of the spectrum, or if the user is willing to put up with the inconvenience of a cryogenic detector, considerable improvement is possible (SS). The pyro-electric detector does not yet seem to offer any advantage for the standard dispersion spectrometers, but it is the heart of the high performance Fourier spectrometer. It will probably be used in a variety of schemes for multiplexing a number of wavelengths onto one detector which appears to have been stimulated by the success of the Fourier spectrometer. Multiple Internal Reflection. The multiple internal reflection probe (561)

which dips into the sample to be analysed looks very interesting, especially for continuous monitoring of process streams. This is a n example of a paper which was not caught by the infrared search profile. However, for this general subject, it would have been feasible to search the entire data base with terms such as multipb internal or i n h n a l refiction without danger of receiving many false hits.

Effect of Particle Size on Infrared Spectra. More papers have appeared concerning the effect of particle size on spectra (818, 819). This is a n effect which shows up only for very strong absorption bands of inorganic solids. The effect also is evident in the spectra of massive samples at highly oblique incidence, and with the electric vector in the plane of incidence. A new band appears as the angle of incidence increases, always at a higher frequency than the band which is measured a t normal incidence. The new band is associated with the longitudinal optical mode of the crystal whose transition moment is perpendicular to the surface (8.41, S47). The reader who is not acquainted with this phenomenon can readily observe it for himself by measuring the spectrum at oblique incidence of a thin piece of silicon whose surface has been oxidized sufficiently to show the 9-micron Si02 band a t normal incidence. This phenomenon is mentioned here to serve as a warning to spectrometrists who may be working with finely powdered inorganic crystals, or who may be measuring spectra of inorganic surface coatings by multiple reflectance spectrometry. Polywater. At the end of t h e last section of the bibliography, the reader will find the results of a computer subsearch on Polywater. Polywater seems to be a different substance in different places, and in no case does it seem to be what the name implies. The whole polywater episode now seems to be another object lesson concerning the amount of care which is required to avoid contamination in handling ultra-small samples. Infrared spectrometrists who deal with microgram and submicrogram samples should take note. BIBLIOGRAPHY

Books ( B l ) Alphabetical List of Compound Names, Formulae, and References to Published Infrared Spectra; an Index to 92,000 Published Infrared Spectra, Amer. Soc. for Testing and Matls., Philadelphia, Pa., 1969, 608 pp; Chem. Abstr., 72,49566q (1970). (B2) The Far Infrared, Handi, A., Presses Univ. of France, Paris, 1969, 260 pp; Chem. Abstr., 72, 49567r (1970). (B3) Infrared Analysis of Chromatographic Microgram Fractions, Copier, H., Druk. Elinkwijk, Utrecht, Neth.,

1968, 72 pp; Chem. Abstr., 72, 74496s (1970). (B4) Basic Infrared Spectroscopy, Van Der Maas J. H., Sadtler Fh. Labs., Philadelpiia, 1969, 108 pp; Chem. Abstr., 72, 127194h (1970). (B5) Atlas of Infrared Spectra of Steric Isomers of Decahydroquinoline Derivativea, Agashkin, 0. V., et al., Nauka, Alma-Ata, 1969, 114 pp; Chem. Abstr., 73,30578~(1970). (B6) Atlas of the Near Infrared Spectra of Venus, Mars, Ju iter, and Saturn, Connes, J., Connes, Maillard, J. P., C.N.R.S., Paris, 1969, 475 pp; Chem. Abstr., 73,30579~(1970). (B7). Infrared Spectra of 2,1,3-BenaothiadiaaoleDerivative.9, Korobkov, V. S., Pesin, V. G., Zubanova, L. P., Nauka, MOSCOW, 1969, 152 pp; Chem. Abstr., 73,30581q (1970). (B8) Hydration and Intermolecular Interaction; Infrared Investigations with Polyelectrolyte Membranes, Zundel, G., Academic Press, New York, 1969, 310 pp; Chem. Abstr., 73, 40368q (1970). (B9) Infrared Spectroscopy; Principles, Applications, Methods (Chemical Monographs, Vol. 5), Kemmner, G., Franckh, Stuttgart, 1969, 125 pp; Chem. Abstr., 73,40369r (1970). (B10) Spectrophotometry in the Far Infrared, Coste, A., Centre Etudes Nucl., Saclay, Fr., 1968, 188 pp; Chem. Abstr., 73,50658~(1970). ( B l l ) Infrared Absorption Spectra of Polymers and Auxiliary Materials, Chulanovskii, V. M., Ed., Khimiya, Leningrad, 1969, 356 pp; Chem. Abstr., 73,88579m (1970). (B12) Infrared Band Handbook, 2nd ed., Szymanski, H. A., Erickson, R. E., Plenum, New York, 1970, 1491 pp; Chem. Abstr., 73,93527~(1970). (B13) Infrared Spectra of Inorganic and Coordination Com ounds, 2nd ed., Nakamoto, K., &ley-Interscience, New York, 1970, 376 pp; Chem. Abstr., 73, 114910j (1970). (B14) Infrared S ectroscopy: Experimental Methogs and Techniques, Stewart, J. E., Dekker, New York, 1970, 656pp; Chem. Abstr., 73, 114911k (1970). (B15) Atmospheric Trans arency in the Visible and the Infrarea, Zuev, V. E., CFTSI, Springfield, Va., 1970, 215 pp; Chem. Abstr., 74,8263m (1971). (i316) Semiconductors and Semimetals, Vol. 5: Infrared Detectors, Willardson, R. K., Beer, A. C., Ed., Academic New York, 1970, 552 pp; Chem. Abstr., 74, 172152 (1971). (B17) An Introduction to Spectroscopic Methods for the Identification of Organic Compounds, Vol. 1: Nuclear Magnetic Resonance and Infrared S ectroscopy, Scheinmann, F., Ed., Pergamon, Elmsford, N.Y., 1970, 201 pp; Chem. Abstr., 74, 19166h (1971). (B18) Chemical Applications of Far Infrared Spectroscopy, Finch, A., et al., Academic, New York, 1970, 277 pp; Chem. Abstr., 74, 26586y (1971). (B19) Far-Infrared Spectroscopy (Pure and Applied Optics), Moeller, K. D., Rothschild, W. G., Interscience, New York, 1970, 752 pp; Chem. Abstr., 74, 70150a (1971). (B20) Far-Infrared Techniques (Ap lied Physics Series), Kimmitt, M. F., $ion, London, England, 1970, 153 pp; Chem. Abstr., 74, 81694g (1971). (B21) Infrared Va or S ectra, Welti, D., Sadtler ResearcE LaEs., Philadelphia, 1970, 211 pp; Chem. Abstr., 74, 8169531 (1971).

fi.,

(B22) IR; Theory and Practice of Infrared S ctrosco y * 2nd ed., Al ert N. L.. geiser. E.. szvmanski. A.: Plenum, New Yoik, "1970, 380 pp; Chem. Abstr., 74, 105582~(1971). (B23) Far-Infrared Properties of Solids . (OFtical Physics a i d Engineering), Mitra. S. S.. Nudelman. S.. Ed.. Plenum, New' York, 1970, ~5 pp'; Chem. Abstr., 74,118253r (1971). (B24) Far-Infrared Techniques, Kimmitt, M. F., Pion, London, 1970. 153 DD: Chem. Abstr.,'74, 149052d (1971). ' (B25) The Aldrich Library of Infrared S ectra, Pouchert, C. J. Aldrich Cfmm. Co., Milwaukee, $is., 1970, 1203 pp; Chem. Abstr., 75, 13421m (1971). (B26) Infrared Spectroscopy: Principles, Uses, Interpretation (Methods of Analysis in Chemistry, Vol. ll), Hediger, H., Akad. Verlagsges, Frankfurt, Germany, 1971, 250 pp; Chem. Abstr., 75, 13425r (1971). (B27) Low-Frequency Vibrations of Inorganic and Coordination Compounds, Ferraro, John R., Plenum, New York, 1971, 303 pp; Chem. Abstr., 75, 13426s (1971). (B28) Modern Practices in Infrared Spectroscopy, Stine, K. E Beckman 1970, Instruments, Fullerton, &if., 642 pp; Chem. Abstr., 75, 13429v (1971). (B29) Vibration Spectra of Pol atomic Molecules, Sverdlov, L. M., govner, M. A., Krainov, E. P., Nauka, Moscow, 1970, 559 pp; Chem. Abstr., 75, 13431q (1971). (B30) Infrared Spectroscopy: Applications in Organic Chemistry, Avram, M., Mateescu, G. D., Dunod, Paris, Fr., 1971, 642 pp; Chem. Abstr., 75, 28155b (1971). (B31) The Spectra and Structutes of Sim le Free Radicals. An Introduction to holecular Spectroscopy, Heraberg, G., Cornel1 Univ. Press, Ithaca, N.Y., 1971, 226 pp; Chem. Abstr., 75, 28159f (1971). (B32) Inorganic Vibrational Spectroscopy, Jones, L. H., Dekker, New York, 1971, 256 pp; Chem. Abstr., 75, 43005w (1971). (B33) Infrared Spectra of Labeled Compounds, Pinchas, S., Laulicht, I., Academic, New York, 1971, 386 pp; Chem. Abstr., 75,43013~(1971). (B34) Far-Infrared Spectroscopy (Series in Pure and Applied Optics), Moller, K. D., Rothschild, W. G., Interscience, Chichester, Engl., 1971, 818 pp; Chem. Abstr., 75,69450n (1971). (B35) Lattice Resonance of Alkali Halides; Far Infra-Red Meawrements at High Temperatures (Studies in Chemistry, Polymer Science, Vol. 4), Mooij, J. E., Rotterdam Univ. Press, Rotterdam, Neth., 1970, 145 pp; Chem. Abstr.,.75, 82312p (1971). (B36) Applications of Infrared Spectroscopy in Biochemistry, Biology, and Medicine, Parker, F. S., Plenum, New York, 1971, 561 pp; Chem. Abstr., 75,105992b (1971). (B37) Infrared Analvsis of Essential Oils.

4.

2

i on Infrared Spectrometry for a Forensic Analyst, De Faubert Maunder, M. J., Hilger, London, England, 1971, 239 pp; Chem. Abstr., 75, 116970~(1971). (B39) Vibrating Molecules: An Introduction to the Interpretation of Infrared and Raman Spectra, Gans, P., Chapman and Hall, London, Eng., 1971, 248 pp; Chem. Abstr., 75, 135740k (1971).

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(B40) Serial Number List of Compound Names and References to Published Infrared Spectra, Suppl. 14 (Atomic and Molecular d a t a Series, 32-S14), Amer. SOC. for Testing and Matl., Philadelphia, Pa., 1971, 102 pp; Chem. Abstr., 75, 146127s (1971). (B41) Molecular Formula List of ComNames, and References to E % & Infrared c l Spectra, Sup 1. 14 (Atomic and Molecular Data 8eries, 31-514) Amer. Soc. for Testing and Matl., bhiladelphia, Pa., 1971, 94 pp; Chem. Abstr., 75, 156943~ (1971). (B42) Infrared-Absorption Spectrometric Methods, Shimauchi, T., Nankodo, Tokyo, Japan, 1971, 164 pp; Chem. Abstr., 75, 157954%(1971). (B43) Infrared Spectra of Inorganic Compounds, N quist, R. A., Kagel, R. O., Academic $rem, 1971. Reviews (Rl) Molecular Dynamics of Polymers as One- and Three-Dimensional Crystals. Calculation of the Specific Heat and Inelastic Neutron Scattering Spectra, Zerbi, G., Corsi Semin. Chim., 1968, 252-4; Chem. Abstr., 72, 3781c (1970). (R2) A Priori Calculation of the Infrared Spectra of Polymers. Study of Molecular Conformation from Analysis of the Vibrational Spectra, Zerbi, G., Corsi Semin. Chim., 1968, 250-1; Chem. Abstr., 72,3811n (1970). (R3)Infrared Spectroscopy, Kim, T. R., Hwahak Kwa Kongop Ui Chinbo, 9, 16-28 (1969); Chem. Abstr., 72, 168491 (1970). (R4) Infrared Characterization of Structural Changes in Polymers, Luongo, J. P., Appl. Polym. Symp., 1969, 121-9; Chem. Abstr., 72,32513~(1970). (R5) Far Infrared Spectra and Lattice Vibrations of Inorganic Complex Salts, Nakagawa, I., Coord. Chem. Rev., 4, 423-62 (1969); Chem. Abstr., 72, 37217 (1970). (R6) Vi i ration Spectra of Polyethylene, Tasumi, M., Kobunshi, 18, 685-92 (1969): Chem. Abstr., 72, 44158y (1970). (R7) Zeolite Study. I. Infrared Spectro hotometry, Kermarec, J., Tempere, J. Imelik, B., Bull. SOC.Chim. Fr., 1969, 3792-7; Chem. Abstr., 72, 49157g (1970). (R8) Infrared Solvent Shifts and Molecular Interactions, Oi, N., Bunko Kenkyu, 18, 194-201 (1969); Chem. Abstr., 72,49158h (1970). (R9) Infrared Reflection Spectra of Thin Films on Metal Surfaces, Suetaka, W., Bunko Kenkyu 18, 187-93 (1969); Chem. Abstr., 72,4926811 (1970). (R10) Analysis of Paints. I. Valero, F., Double Liaison, 1969, 369-72; Chem. Abstr., 72, 56743y (1970). (R11) Infrared Astronomy, Webbink, R. F., Jeffers, W. Q., Space Sci. Rev., 10, 191-216 (1969); Chem. Abstr., 72, 72630q (1970). (R12) Infrared Spectroscopy, Smith, C. D., Treatise Coatings, 2, 429-500 (1969); Chem. Abstr., 72, 72632s (1970). (R13) Generation of Far-Infrared Radiation, Robinson, L. C., Advan. Electron. Electron Phys., 26, 171-215 (1969); Chem. Abstr., 72, 72634u (1970). (R14) Effect of Molecular Interactions on the Infrared Spectra of Proton Donors, Josien, M. L., Lascombe, J., Colloq. Spectrosc. Int., Ottawa, 13th 1967,40-57 (Publ. 1968); Chem. Abstr., 72, 72635v (1970). (Rl5) MIR Infrared Spectroscopy in Skin Analysis, Ferren, W. P., Amer. Perfum. Cosmet., 84, 27-36 (1969); Chem. Abstr., 72,75404e (1970).

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(R16) Interferometric Instruments for Far Infrared Spectroscopy. II., Parrett, F. W., Lab. Pract., 19, 177-9 (1970); Chem. Abstr., 72, 84347r (1970). (R17) Conformational Isomerism of the Amide Group-A Review of the I R and NMR Spectrosco ic Evidence, M., J . Mol. Hallam, H. E., Jones, Stmct., 5, 1-19 (1970); Chem. Abstr., 72,84355s (1970). (R18) New Ways in Research of Molecules, Fogarasi, G., Termeszet Viilaga, 100, 514-17 (1969); Chem. Abstr., 72, 84359w (1970). (R19) Nondispersive Infrared Analysis of Gases, Luft, K. F., Haus. Tech., Essen, Vortragsveroeff., 1967, 22-31; Chem. Abstr., 72,85814~(1970). (R20) Infrared Spectro hotometry (in the Paint Industry), fwinehart J. S., Hannah, R. W., Perkins, dv. D., Ind. Finish. (London), 21, 34 (1969); Chem. Abstr., 72,91511t (1970). (R21) Exploring the Excitation S ectra of Crystals Using Far Infrared iadiation, Sievers, A. J., Elem. Excitations Solids, 1969, 193-258; Chem. Abstr., 72,94673h (1970). (R22) Theoretical and Ex erimental Asects of Localized and &eudolocalized bhonons, Maradudin, A. A,, Elem. Excitations Solids, 1969, 35-65; Chem. Abstr., 72, 94674j (1970). (R23) Infrared Absorption Spectra of Organophosphorus Compounds, Nakayama, J., Yuki Gosei Kagaku Kyokai Shi, 28, 132-43 (1970); Chem. Abstr., 72,94678~(1970). (R24) Infrared Spectra of Inorganic Compounds in the 500-33/cm Region, Feairheller, W. R., Jr., Miller, J. T., Jr., U.S. Clearinghouse Fed. Sci. Tech. Inform., AD 1969, AD-697992, 60 pp; Chem. Abstr., 72,94689t (1970). (R25) Infrared Spectroscopic Method of Moisture Measurement, Pande, A., Chem. Process. Eng. (Bombay), 2, 31-7 (1968); Chem. Abstr., 72, 96204e (1970). (R26) Infrared Spectroscopy for Identifying Surfactants, Nettles, J. E., T e d . Chem. Color. 1. 430-41 (1969): Chem. Abstr., 72, 102686m (1970j.- - - ’ ’ (R27) Infrared and Raman Studies on Molecular Structure and Motion in Condensed Phases, Wilkinson, G. R., Nut. Bur. Stand. ( U S . ) , NBS-SpecPubl-301, 77-133 (1969); Chem. Abstr., 72, 105330~(1970). (R28) New Results of Investigations on the Structure of Coal by Spectroscopic SpectrosMethods. I. Absorption copy in the Ultraviolet, Visible, and Infrared Regions, Oelert, H. H., Hemmer, E. A., Erdoel Kohle, Erdgas, Petrochem., 23, 87-91 (1970); Chem. Abstr., 72, 113543j (1970). (R29) Experimental Techniques for the Study of Surface Phenomena in Heterogeneous Catalysis, Jiru, P., Chim. Ind. (Milan), 52, 128-34 (1970); Chem. Abstr., 72, 115169r (1970). (R30) Infrared Study of Transient Molecules in Chemical Lasers, Pimentel, G. C., Pure Appl. Chem., 18, 275-84 (1969); Chem. Abstr., 72, 116162~ (1970). (R31) Scientific Methods in Art and Archaeology, Werner, A. E., Chem. Brit., 6 , 55-9 (1970); Chem. Abstr., 72, 117469n (1970). (R32) Space Use of High Polymers, Ashikari, N., Shinku Kagaku, 16, 123-30 (1969); Chem. Abstr., 72, 122466~ (1970). (R33) Use of Infrared Spectroscopy in the Textile Field, Prati, G., Tinctoria, 65, 313-18 (1968); Chem. Abstr., 72, 122680d (1970).

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(R34) Vibrational S ectra of Organotin and Organolead Sompounds, Tanaka, T., Organometal. Chem. Rev., Sect. A , 5, 1-51 (1970); Chem. Ab&., 72, 126731~ -~~ . - (1970). - - ,(R35) New Infrared Detectors, Putley, E. H., Advan. Geophys., 1970, 129-63; Chem. Abstr., 72, 127183d (1970). (R36) Far Infrared Vibrational Spectroscopy, Molecular Potentials, Theimod namic Functions, Spangenberg, H. J., Zunath, D., 2. Chem., 10, 87-101 (1970); Chem. Abstr., 72, 137922h (1970). (R37) Infrared S ectrometry. Research Technique in t i e Cement Chemistry, Vazquez Moreno, T., Mater. Constr., Ultimos Avan., 1969, 37-44; Chem. Abstr., 73, 6827d (1970). (R38) Application of Infrared Spectroscopy to the Study of Adsorption and Mechanism of Catalytic Reactions, Cukr, M., Chem. Listy, 64, 337-65 (1970); Chem. Abstr., 73, 18884h (1970). (R39) Infrared Gas Analyzer, Oshiman, T., Nenryo Oyobi Nensho, 37, 241-53 (1970); Chem. Abstr., 73, 19827d (1970). (R40) Infrared Spectroscopy, Orr, S. F. D., Spectroscopy, 1969, 32-5; Chem. Abstr., 73, 19828e (1970). (R41) Far Infrared Spectroscopy, Hadni, A., Opt. Spectra, 4, 57-9 (1970); Chem. Abstr., 73, 19836f (1970). (R42) Optical Properties of Nickel and Iron Carbonyls, Fedorova, G. R., Tr. Proekt. Nauch.-Issled. Inst. “Gipronikel” (Gos. Inst. Proekt. Predar. Nikelevoi‘ Prom.), 1968, 140-8; Chem. Abstr., 73, 19837g (1970). (R43) Infrared Spectrometry, Crisler, R. O., ANAL. CHEM., 42, 388R-397R (1970); Chem. Abstr., 73, 19841d (1970). (R44) Infrared Absorption S ectrosco y in Organic Analysis, Roccliccioli, Chim. Anal. (Paris), 52, 273-82 (1970); Chem. Abstr., 73,21112k (1970). (R45) Spectroscopic Study of the Carotenoid Structure, Tamas, V., Stud. Cercet. Chem., 18, 137-59 (1970); Chem. Abstr., 73,25703b (1970). (R46) Study of Metal Surfaces by Infrared Spectroscopy, Suetaka, H., Kinzoku, 40, 74-7 (1970); Chem. Abstr., 73, 28089s (1970). (R47) Infrared Spectroscopy, Ulrich, W. F., Opt. Spectra, 4, 38-44 (1970); Chem. Abstr., 73,30205~(1970). (R48) Combined A lication of ThinLayer and Paper egromatography and Spectroscopy in the Microgram Range. Introduction, Szekely, G., J. Chromatogr., 48, 313-21 (1970); Chem. Abstr., 73,31170s (1970). (R49) Infrared Absorption Spectrosco y and the Analysis of Macromolecukr Products, Mihaila, D., Costea, M., Ind. Usoara, 17, 147-54 (1970); Chem. Abstr., 73,35780~(1970). (R50) Infrared Radiators in Fixation Procedures in Textile Finishing, Krentz, V., Ilg, H., Bechter, D., Tezt.-Prax., 25, 168-72 (1970); Chem. Abstr., 73, 36347q (1970). (R51) Fourier Transform Spectroscopy, Low, M.J. D., iVaturwissenschaften, 57, 280-7 (1970); Chem. Abstr., 73, 50189w (1970). (R52) Numerical Shape Analysis of I R Absorption Bands, Hawranek, J. P., Waad. Chem., 24, 225-42 (1970); Chem. Abstr., 73, 50352~(1970). (R53) Fourier Transform Spectrometers. 3, Low, M. J. D., J. Chem. Educ., 47, A415-A416 (1970); Chem. Abstr., 73, 60668r (1970). (R54) Infrared Absorption Intensities, Higuchi, S., Kagaku Kogvo, 21, 929-36 \ - -

e.,

(1970); Chem. Abstr., 73, 60679v (1970). (R.55) Quantitative Analysis by Infrared Spectrophotometry, Perry, J. A., Appl. Spectrosc. Rev., 3, 229-61 (1970); Chem. Abstr., 73,62220n (1970). (R56) Infrared (10-1000 Mu) Celestial Sources, Melchiorri, F., MelchiorriOlivo, B., Quad. “Ric. Sci.” 1968, Chem. Abstr., 73, 71460t 151-70; (1970). (R57) Fundamental Elements of Infrared S ectroscopy in the Study of Secondary dinerals and the Organic Matter of the Soil, Prost, R., Bull. Ass. Fr. Etude Sol, 1970, 19-29; Chem. Abstr., 73, 901142 (1970). (R58) Analysis in Molecular SpectrosCODV (NMR. EPR. In,. Yamamoto. T.:#Fujiwara; ST, Bunsek; Kagaku, 19; 715-21 (1970); Chem. Abstr., 73, 92846p (1970). (R59) Application of Infrared Spectroscopy to the Study of Silicates, Prost, R., Ann. Agron., 20, 547-64 (1969); Chem. Abstr., 73, 92850k (1970). (R60) Application of Ultraviolet and Infrared Spectroscopy to the Study of Protein Structure, Elodi, P., Zavodszky, P., Magy. Tud. Akad. Biol. Tud. Oszt. Kozlem., 12, 381-416 (1969); Chem. Abstr., 73,94481q (1970). (R6l) Birefringence and Infrared Dichroism of Crystalline High Polymers, Asada, T., Kogyo Kagaku Zasshi, 73, 1303-11 (1970); Chem. Abstr., 73, 99213p (1970). (1162) Study of Chlorites by Means of New Techniques, Caillere, S., Trav. Com. Int. Etude Bauxites, Oxydes, Hydroxydes Alum, 1969, 1-12; Chem. Abstr., 73, 100848h (1970). (R63) Far-Infrared Spectra of Color Centers in Alkali Halides, Baeuerle, D., Fritz, B., Radiat. EP., 4, 155-9 (1970); Chem. Abstr., 73, 103642~(1970). (1164) Attenuated Total Reflection Method, Tanaka, S., Kagaku Kogyo, 21, 922-8 (1970); Chem. Abstr., 73, 103645a (1970). (R65) Improved Double Beam Vacuum Far-Infrared S ectrophotometer. Model FIS-3 Hitachi far-Infrared Spectrophotometer, Iwahashi, I., Matsumoto, K., Matsudaira, S., Hitachi Rev., 18, 326-35 (1969); Chem. Abstr., 73, 103646b (1970). (1166) Far-Infrared Spectroscopy, Rothschild, W. G., Moeller, K. D., Phys. Todav, 23. 44-9 (1970): Chem. Abstr., 73, 103647~(1970). (R67) Industrial Applications of Infrared Spectrophotometer, Rao, P. H., Indian Chem. Mfr., 8, 9-13 (1970); Chem. Abstr., 73, 103652a (1970). (IL.68) Infrared Spectroscopic Determination of the Association Constants of Hydrogen Bonds, Adamek, P., Ksandr, Z., Sb. Vys. Sk. Chem.-Technol. Praze, Anal. Chem., 1969, 91-100; Chem. Abstr., 73, 103661~ (1970). (R69) Applications of Infrared Spectroscopy to the Study of the Adsorption and of the Mechanism of Catalytic Reactions. 11, Cukr, M., Chem. Listy, 64, 785-809 (1970); Chem. Abstr., 73, 11455913 (1970). (IL.70) Infrared Ray Identification of Textile Fibers, Schneegluth Cugat, C., Textila, 46, 28-37 (1970); Chem. Abstr., 73, 121407d (1970). (ll.71) Raman and Infrared Spectroscopy of Concentrated Electrolyte Solutions and Fused Salts, Hester, R. E., Annu. Rep. Progr. Chem., Sect. A , 1970, 79-91; Chem. Abstr., 73, 125088~ (1970). (Il.72) Temperature Measurement by Infrared Radiation, Bulkley, D., In-

strum. Contr. Syst., 43, 91-3 (1970); Chem. Abstr., 73, 12510Ow (1970). (R73) Technology and Design of Gallium Arsenide Laser and Non-Coherent IREmitting Diodes. 1, Glicksman, R., Solid State Technol., 13, 29-35 (1970); Chem. Abstr., 73,135419~(1970). (R74) Infrared Spectroscopy and Ultraviolet Circular Dichroism Studies of Proteins and Polypeptides in Aqueous Solutions, Timasheff, S. N., Stevens, L., Trans. Bose Res. Inst., Calcutta, 31, 75-86 (1968); Chem. Abstr., 73, 135422s (1970). (R75) Infrared Spectroscopy in Modern Experimental and Theoretical Chemistry, Schutte, C. J. H., S. Afr. Chem. Process., 4, 87-91 (1969); Chem. Abstr., 73, 13542.7~(1970). (R76) Application of Infrared Absorption -4nalysis to the Analysis of Steels, Yamaguchi, N., Sato, K., Kinzoku, 40, 82-5 (1970); Chem. Abstr., 73, 136944a (1970). (R77) Use of Infrared Absorption to Analyze Trace Impurities of Harmful Substances in Air, Korablev, I. V. Lositskii, I. T., Matsnev, V. M., Melamed, A. G., Rylov, V. A., Zh. Vses. Khim. Obshchest., 15, 837-42 (1970); Chem. Abstr., 74, 6217a (1971). (R78) Role of Resonance Interactions in Some Molecular Far-Infrared Laser Systems, Kessler, X. G., Comments At. Mol. Phys., 2, 67-72 (1970); Chem. Abstr., 74, 7895g (1971). (R79) Problems of Mineralogical Study, Rozhkova. E. V.. Sovrem. Metodu Mineral. issled., 1969, 5-16; Chek. Abstr., 74,14819~(1971). (R80) Low-Level Coherent and Incoherent Detection in the Infrared, Keyes, R. J., Quist, T. 11.)Semicond. Semimetab, 1970, 321-59; Chem. Abstr., 74, 25889n (1971). (R81) Pyroelectric Detector, Putley, E. H., Semicond. Semimetals, 1970, 259-85; Chem. Abstr., 74,2589Of (1971). (R82) Indium Antimonide Photoconductive and Photoelectromagnetic Detectors, Kruse, P. w., Semicond. Semimetals, 1970, 15-83; Chem. Abstr., 74,26283~(1971). (R83) Application of Infrared Spectroscopy to the Study of Adsorption on Metals, Grecu, R., Stud. Cercet. Chim., 18, 815-31 (1970); Chem. Abstr., 74, 34951d (1971). (R84) Applications of Superconductors at High and Very High Frequencies, Septier, A., J . Ing., 19, 14-16 (1970); Chem. Abstr., 74, 35848x1 (1971). (R8.5) Application of Infrared Spectroscopy to Surface Coatings, McKay, T. R., Aust. Paint. J., 16, 9-11 (1970); Chem. Abstr., 74,43549f (1971). (R86) Characterization of Surface States by Infrared Spectroscopy, Fripiat, J. J., Bull. SOC. Chim. Fr., 1970, 3285-90; Chem. Abstr., 74,47379~(1971). (R87) Infrared Spectroscopy of Chemisorbed Molecules, and Some Problems of Catalysis, Filimonov, V. N., Probl. Kinet. Katal., 1970, 32-44; Chem. Abstr., 74,47380s (1971). (R88) Infrared Drying of Synthetic Resin Coatings, Przibram, A., 1nd.-lackierBetr., 38, 537-9 (1970); Chem. Ahstr., 74,55i90v (1971). (R89) Infrared Spectra and Structure of Borates, Povarennykh, A. S., Idei E. S . Fedorova Socrem. Kristallogr. Mineral., 1970, 118-36; Chem. Abstr., 74, 58713d (1971). (R90) Infrared Absorption Spectroscopy, Tanaka, Y . , Nippon Gomu Kyokaishi, 43, 966-74 (1970); Chem. Abstr., 74, 65196r (1971). (R91) Infrared Spectroscopic Study of the Nature of Physical Adsorption

Centers, Filimonov, V. N., Osn. Prohl. Teor. Fiz. Adsorbtsii, Tr. Vses. Konf. Teor. Vop. Adsorbtsii, 1st 1968, 116-3i (Publ. 1970); Chem. Abstr., 74, 68032~ (1971). (R92) Far-Infrared Absorption Spectrum of Liauid Water. Andreev. D. V.. Gal’tsev, A. P., ‘Probl. Fi;. Atmosl: 1970, 56-69; Chem. Abstr., 74, 69561d (1471 \-”.-,.\

(R93) Use of Infrared Spectroscopy for Studying the Structure of PhenolFormaldehyde Resins, Pshenitsyna, V. P., Shabadash, A. N., Phst. Massy, 1970, 199-205; Chem. Abstr., 74, 76877q (1971). (R94) Properties of Thin Films of Silicon Nitride, Zaleska, T., Goral, H., Elektronika, 11, 331-5 (1970); Chem. Abstr., 74,80827r (1971). (R95) Methods for Calculation of Spectral Absorption of Infrared Radiation by Atmospheric Gases, Moskalenko, N. I., Mirumyants, S. O., Izv. Akad. iVauk SSSR, Fiz. Atmos. Okeana, 6 , 1110-26 (1970); Chem. Abstr., 74, 89573n (1971). (R96) Infrared Spectroscopy, Pock, H., Oesterr. Apoth. Ztg., 24, 819-23 (1970); Chem. Abstr., 74,91205n (1971). (R97) Improvement in Semiconducting Detectors for Infrared Regions. Arai. T.. Oyo Butsuri, 39, 806-23 71970); Chem: -4bstr., 74, 92822y (1971). (R98) Automatic Measurement of the Fat and Protein Contents of Milk, Green, E., J . SOC.Dairy Technol., 23, 190-5 (1970); Chem. Abstr., 74, 9822413 (1971). (R99) Oxygen Content Determination in Thin Silicon Slices, Szep, I., Barsony, I., Acta Phys., 29, 97-106 (1971); Chem. Abstr., 74, 104277q (1971). (R100) Fermi Resonance in I R and Raman Spectra, Tylli, H., Suom. Kemistiseuran, Tiedonantoja, 79, 39-42 (1970); Chem. Abstr., 74, 104815~ (1971). (RlOl) Terrestial Radiation and Horizon Sensors, Desvignes, F., Acta Eleclron., 13, 227-47 (1970); Chem. Abstr., 74, 1 0 4 8 2 9 ~(1971). (R102) Infrared and Raman Spectra. I., Shimanouchi, T., Kagaku iVo Ryoiki, 25, 89-95 (1971); Chem. Abstr., 74, 104832s (1971). (R103) Correlation of Solvent Effects on Physical and Chemical Pro erties, Katritzky, A. R., Fowler, F. W., lutherford, J. D., J. Chem. SOC.B, 1971,460-9; Chem. Abstr., 74, 111426r (1971). (R104) Fa:-Infrared Absorption S ectra of Apatite and Pyromorphite, &no$ K., Kobvtsugaku Zasshi, 9, 219-34 (1969); Chem. Abstr., 74, 114117b (1971). (R105) Application of Spectroscopy in the Study of Glassy Solids. 11. Infrared, Raman, EPR, and NMR Spectral Studies, Wong, J., Angell, C. A., Appl. Spectrosc. Rev., 4, -155-232 (1971); Chem. Abstr., 74, 117oo3b (1971). (R106) Sha es of Infrared Absorption Bands of Liquids, Jones, R. N., Young, R. P., Chem. Rev., 71, 219-28 (1971); Chem. Abstr., 74, 117562d (1971). (R107) Prospects of Bpplying Infrared Spectrometry in Pharmaceutical Analysis, Shilov, Y. U. SI.,Verem’ev, I. V., Farmatsiya (Moscow), 20, 76-82 (1971); Chem. Abstr., 74, !30410x (1971). (R108) Spectroscopic Studies in Surface Chemistry, Smart, R. St. C., Proc. Roy. Aust. Chem. Inst., 37, 344-8 (1970); Chem. Abstr., 74, 130695~ (1971). (R109) Preparation and Properties of Infrared-to-Visible Conversion Phosphors, Qstermayer, F. W., Jr., Met. Trans., 2, 747-55 (1971); Chem. Abstr., 74, 131581r (1971).

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(R110) Infrared Spectrosco ic Study of the Ability of the Cargonyl Group to Form Two Hydrogen Bonds in Solution, Combelas, P., Garrigou-Lagrange, C., Lascombe, J., Ann. Chim. (Paris),5,315-25 (1970); Chem. Abstr., 74, 148389g (1971). (R111) Infrared Spectra Molecules, Papousek, D., Sovicka, R., Vesmir, 49, 356-8 (1970); Chem. Abstr., 74,1484OOd (1971). (R112) Infrared Methods, Fraser, R. D. B., Suzuki, E., Ph.jls. Principles Tech. Prolein Chem., 1970, 213-73; Chem. Abstr., 75, lOlOp (1971). (R113) Infrared Spectrophotometry for Pesticide Industry Quality Control, Glab, A., Matuszewska, E., Szymaszkiewicz, J., Przem. Chem., 50, 178-80 (1971); Chem. Abstr., 75, 4445v (1971). (R114) Instruments for Measurin Sulfur Dioxide in Waste Gases, Tanafa, M., Nenryo Oyobi Nensho, 38, 129-35 (1971); Chem. Abstr., 75, 9602d (1971). (R115) Infrared Lasers, Patel, C. K. N., Develop. Laser Technol., Semin.-Depth, PTOC.1969, 49-59 (Publ. 1970); Chem. Abstr., 75, 12471r (1971). (R116) Matrix Isolation, Ogden, J. S., Turner, J. J., Chem. Brit., 7, 186-90 (1971); Chem. Abstr., 75, 124792 (1971). (R117) Intramolecular Bonding of Hydrogen in Hydroxysteroids. Infrared Spectral Study, Hodosan, F., Ciurdaru, V., Mantsch, H., Stud. Cercet. Chim., 19, 191-210 (1971); Chem. Abstr., 75, 12482~(1971). (R118) Infrared Absorption Spectra of Aliphatic Nitro Compounds and their Derivatives, Slovetskii, V. I., Usp. Khim., 40, 740-63 (1971); Chem. Abstr., 75, 124931 (1971). (R119) Diffuse Reflectance S ectroscopy in the Infrared Region, d m i y a , M., Kagaku No Ryoiki, 25, 200-8 (1971); Chem. Abstr., 75, 12512e (1971). (R120) Infrared and Raman Spectra, Shimanouchi, T., K aku No Ryoiki, 25, 187-92 (1971); Them. Abstr., 75, 12514 (1971). (R121) nfrared and Raman Spectra. 111.. Shimanouchi. T.. Kaaaku No Ruoiki. 25. 275-80 (19711: Chem. ~ i ~ t r . , ’ 7limb 5, (i971j. (R122) Recent Infrared and Far-Infrared Spectrophotometer, Iwahashi, I., Kagaku No Ryoiki, 25, 107-16 (1971); Chem. Abstr., 75, 12519n (1971). (R123) Infrared AbsorDtion SDectra of ‘ High Molecular weight Polymers, Tadokoro, H. Yokoyama, M., Sen-i TO Kogyo, 3, 603-11 (1970); Chem. Abstr., 75, 21028d (1971). (R124) Lasers: From Far-Infrared to Ultraviolet, Ywan, M., Recherche, 2, 372-3 (1971); Chem. Abstr., 75, 27333w 1. I1971 - -,(R125) Molecular Spectra of Hydrocarbons: Electronic, Vibrational, and Proton Magnetic Resonance Spectra, Casu, B., Riv. Combust., 25, 112-29 (1971); Chem. Abstr., 75, 27351a (19711. (R126) Infrared Spectroscopy. Analysis of Molecular Motion, Van Der Maas, J. H., Chem. Weekbl., 67(16), A33-A34 (1971); Chem. Abstr., 75, 29504b (1971) ,- . - ,. (R127) Molecular Spectrosco y Dijkstra, A27-A29 G., Chem. Weekbl., 67(1’f!), (1971); Chem. Abstr., 75, 29505c (1971). (R128) ExDlorinn Solids with Far Infra. red Rad