Infrared Spectra and Characteristic Frequencies of Inorganic Ions

Their Use in Qualitative Analysis

FOIL A. MILLER AND CHARLES H. WILKINS Department of Research in Chemical Physics, Mellon Institute, Pittsburgh 13, Pa.
Polyatomic ions exhibit characteristic infrared spectra. Although such spectra are potentially useful, there is very little reference to them in the recent literature. In particular, the literature contains no extensive collection of infrared spectra of pure inorganic salts obtained with a modern spectrometer. In order to investigate the possible utility of such data, the infrared spectra of 159 pure inorganic compounds (principally salts of polyatomic ions) have been obtained and are presented here in both graphical and tabular form. A table of characteristic frequencies for 33 polyatomic ions is given. These characteristic frequencies are shown to be useful in the qualitative analysis of inorganic unknowns. Still more fruitful is a combination of emission analysis, infrared examination, and x-ray diffraction, in that order. Several actual examples are given. It is evident that a number of problems involving inorganic salts containing polyatomic ions will benefit by infrared study. The chief limitation at present is the practical necessity of working with powders, which makes it difficult to put the spectra on a quantitative basis.

LTHOUGH there has been a vast amount of work on the Raman spectra of inorganic salts ( 2 , 4 ) , the study of them in the infrared has been relatively neglected. Schaefer and Matossi (10) have reviewed work done up to 1930, most of which deals with reflection spectra. The most extensive surveys of infrared absorption spectra have been made by Lecomte and his coiTorkers (6, 7 ) , but unfortunately many of their data are somewhat out of date and are not always presented in the most useful form. References to studies on a few ions are given in the books by Wu (12) and by Herzberg ( 3 ) . There has recently been renewed interest in the detailed study of the infrared spectra of selected salts, as exemplified by the papers of Halford ( 8 ) , Hornig ( I I ) , and their coworkers. The well known Colthup chart ( 1 ) contains characteristic frequencies for nitrate, sulfate, carbonate, phosphate, and ammonium ions. An excellent recent paper by Hunt, Kisherd, and Bonham ( 5 ) contains the spectra of 64 naturally occurring minerals and related inorganic compounds. Aside from sixteen spectra in this latter paper, there is in the literature no compilation of infrared spectra of inorganic salts obtained with a modern spectrometer. I t therefore seemed worth while to make a fairly extensive survey to seek answers to the following questions: Is it generally possible to obtain good spectra? Do the ions possess frequencies which are sufficiently characteristic to be useful for analytical purposes? What is the effect on the vibrational frequencies of varying the positive ion? Is infrared spectroscopy useful in the analysis of salts? This paper presents the spectra from 2 to 16 microns of 159 pure inorganic compounds, most of which are salts containing polyatomic ions. A chart of characteristic frequencies for 33 such ions is given. The use of these data for the qualitative analysis of inorganic mixtures is demonstrated. Finally, a number of interesting or puzzling features of the spectra are described.

A brief classification of the various types of vibrations in crystals may be appropriate. Ionic solids are considered fiist. In a crystal composed solely of monatomic ions, such as sodium chloride, potassium bromide, and calcium fluoride, the only vibrations are lattice vibrations, in which the individual ions undergo translatory oscillations. The resulting spectral bands are broad and are responsible for the long wave-length cutoff in transmission. I n a crystal containing polyatomic ions, such as calcium carbonate or ammonium chloride, the lattice vibrations also include rotatory oscillations. Of greater interest in this case, however, is the existence of internal vibrations. These are essentially the distortions of molecules whose centers of mass and principal axes of rotation are a t rest. The internal vibrations are characteristic of each particular kind of ion. I n molecular solids, such as benzene, phosphorus, and ice, the units are uncharged molecules held in the lattice by weak forces of the van der Waals type, andoften also by hydrogen bonds. The same classification into internal and lattice modes can be made. A few examples of such solids are represented in this paper (boric acid, and possibly the oxides of arsenic and antimony). Finally there are the covalent solids, such as diamond and quartz, in which the entire lattice is held together by covalent bonds. Here the distinction between lattice and internal vibrations disappears. One might a t first expect an ill-defined and featureless spectrum, but such is not the case. Actually there are bands that are very Characteristic. The situation is in some ways analogous to that in a polymer, which in spite of its size and complexity possesses a remarkably discrete spectrum. Silica gel is the only representative of this type included here.
EXPERIMENTAL

Origin and Preparation of Samples. Practically all the samples were commercial products of C.P. or analytical reagent grade. The samples were gound to a fine powder to minimize the scattering of light, and were examined as Sujol mulls. When there were spectral features that were obscured by the Sujol bands, the samples were either run as a dry powder or mulled in fluorolube (a mixture of completely fluorinated hydrocarbons. Fluorolube is a product of the Hooker Electrochemical Co., perfluoro lube oil of E. I. du Pont de Semours & Co.). Some compounds, such as ferric nitrate nonahydrate (No. 49) and calcium permanganate tetrahydrate ( S o . l50),seemed to mull up in their own water of hydration. When the fine powder x a s rubbed between salt plates, it acquired the appearance and feel of a typical mull, but no appreciable fogging of the salt plates resulted. For other compounds, such as potassium carbonate, breathing on the sample achieved the same result. This is not recommended, however, for it varies the water content unnecessarily, and with potassium carbonate some of the bands are shifted. Although these techniques are satisfactory for qualitative examination, it may be of interest t o list some other methods which have been mentioned in the literature for handling inorganic solids. Lecomte, who introduced most of them, has pointed out that a finely ground dry powder scatters very little radiation of wave length greater than 6 microns and consequently it may be used directly in that region (6, 7 ) . He also suggests coating
1253

1254
Table I.
Formula Boron hletaborate

ANALYTICAL CHEMISTRY
Index to Infrared Curves and Tables of Data
No. 1 2 3
4

Type Sulfur (Contd.) Sulfate

Formula

No.

Tetraborate

5 6

Perborate Misc. Carbon Carbonate

L1&03

7
8 9

Bisulfate Thiosulfate

NazCOz KzCOa 3hfgCOs hlg(OH)n.3HzO CaCOa BaCOa PbCOa SHiHCOa NaHCOa KHCOa NaCN KCY KOCX AgOCN NHISCN NaSCN KSCN Ba(SCN)z. 2Hz0 Hg(SCS)z Pb(SCN)z

coco3

Bicarbonate

10 11 12 13 14 15 16 17 18 19 20

Metabisulfite Persulfate Selenium Selenite Selenate NazSeOa CuSeOa, 2H20 (NHhSeOi NazSeOi. lOHzO KzSeOh CuSeOl. 5HzO NaC108 KClOa Ba(Cl0s)z.Hz0 NHiClOi SaClOa, H20 KClOa Mg(CIO*)z NaBrOa KBr03 AgBrOa

103
104

105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 KIOi 126 127 128 (NHl)zCrOa NazCrOi KzCrOa MgCrO4.7HzO BaCrOb ZnCrOa, 7HzO PbCrOa Alr(CrOd8 (NH4)zCrzOi NazCrtO~. 2H20 KzCrrOr CaCrzOl.3HzO CuCrzOr ,2Hz0 NazMoOi, 2HzO Kd~foOi.5HnO (~Hdahfo7O24.4HzO NanWOi.2HzO KzWOI CaWOi NaMn04.3HzO KMnOi Ca(MnOi)*.lHzO Ba(Mn0h NarFe(CN)a. 10HzO KdFe(CN)o.3Hn0 ca~Fe(CN)a 12Hz0 . KaFe(CN)s NasCo(N0r)o (NHdzCe(N0ah NHhCl BaCln. 2Hz0 Nujol, fluorolube 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160

Cyanide Cyanate Thiocyanate

21 22 23 24

Chlorate

Silicon Metasilicate Silicofluoride Silica gel Sitrogen Nitrite

Perchlorate 31 32

NazSiFs SiOr , XHZO Nah-02 KNO? AgNOz Ba(SOz!z Hz0

33 34 36 36 37 38 39 40 41 42 43 44 45 46 47 48 49

Bromine Bromate Iodine Iodate

Nitrate

Periodate Vanadium Metavanadate Chromium Chromate

Subnitrate Phosphorus Phosphate, tribasic

BiOSOz.Hz0

50

51 52 53 54 55 56 67 58 59 (NHdzHPOi hazHPOi.12HzO KiHPOi MgHPOi. 3Hz0 CaHPOa. 2H20 BaHPOi 60 61 62 63 64 65

Dichromate

Molybdenum Molybdate Heptamolybdate Tungsten Tungstate Manganese Permanganate

Phosphate, dibasic

66 67
68

69 70 71 Orthoarsenate, tribasic Orthoarsenate, dibasic Orthoarsenate, monobasic Oxide Antimony Oxide Sulfur Sulfite Car(.4sOi)z NazHAsO4.7HzO PbnHAsOi KHz.4~04 72 73 74 75 76 77 78 79 80 81 82 83 84

Complex ions Ferrocyanide Ferricyanide Cobaltinitrite Hexanitratocerate Chlorine Chloride Mulling agents

AszO:
SbzOa Sbzos (NHI)ZSOS HzO NazSOa KzSOa 2Hz0 CaSOa 2Hz0 BaSOa ZnSOs 2H20

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2
Table 11.
v w = very weak

1255

Positions and Intensities of Infrared Absorption Bands

s = strong

weak

m = medium Cm. -1

vs =

verystrong s h = shoulder b = broad = KBr region (15-25~) eyamined

vb = verybroad

s p = sharp

imp. = impurity

C m . - 1 Microns I 1. Sodium metaborate NaBOz 862 11 60 w 925 10 80 vs, b 8 50 ni 1175 1310 7 64 rs 1655 6 05 m 3470 2 85 YS, vb
2. M a nesium metaborate

Microns I 9. Boron nitride BN 810 12.35 w 1390 7.2 s

10.

Cm. -1
20. 705 833 990 1010 1370 1410 1630 2380 2600 2950

M%Bo~)~.~H~o
12.4 11.95 11.2 10.5 9.95 9.2 8.8 8.2 7 3 7 05 6 1 2 98 2 86
s m vw
w

864 1445 1490 11. 700 705 855 878 1440 1755 2500 2620 -3000

Lithium carbonate LipCOp 1 1 . 5 8 in 6.92 s 6.7 s Sodium carbonate NapCOa 14.3 in 14.2 m 11.7 v w 11.4 s 6 . 9 5 vs 5.7 m, sp 4.0 m 3 . 8 2 vw 3.3 m, vb

808 838 892 952 1005 1085 1130 1220 1370 1420 1640 3360 3500
3.

hficrons I Potassium bicarbonate KHCOa 14.2 s 12.0 s , s p 10.1 s 9.9 9 m, sh 7.3 vs 7.1 6 . 1 5 vs 4.2 w 3 . 8 5 s , vb 3.37 m

Cm. -1 Microns I 31. Sodium metasilicate NarSiOa. 5Hz0 715 14.0 s 775 12.9 s 832 12.03 s 980 10.2 YS 8.9 m 1125 8.58 m 1165 5.9 m 1695 2330 4.3 m 3280 3 . 0 5 vs, vb 32. Potassium metasilicate KtSiOa 13.0 vw 1 0 . 1 vs, vb 6.15 vw 3.0 m Sodium silicofluoride Na2SiFa 13.73 v s m,sh 12.7 9.05 vw 34. Silica gel SiOz. xHzO 800 948 1090 1190 1640 3330 35. 831 1250 1335 36. 830 1235 1335 1380 2560 3450 37. 833 848 1250 1380 12.5 10.55 9,l5 8.4 6.1 3.0
w w vs

m
s
s

w s s

w s
s

21. Sodium cyanide NaCN (NasCOa impurity) 11.55 m , imp. 865 1310 7 . 6 5 vw 1460 6 . 8 5 vs,imp. 6.1 m 1640 2080 4.8 s 4.5 w, vb 2220 3.0 m , vb 3330 22. Potassium cyanide KCN (KHCOa, K ~ C O S impurities) 1 2 . 0 m , imp. 833 882 11.35 vw, imp. 1440 6 . 9 5 s , imp. 1635 6.12 8 2070 4.83 s 23. Potassium cyanate KOCN (KHCOa impurity) 706 833 980 1010 1210 1310 1410 1640 2130 2630 14.17 12.0 10.2 9.9 8 25 7.65 7.1 6.1 4.7 3.8
s. imp. s,rmp. m, !mp. m , imp. m , sp. n ' , s,p. v s , !mp. vs, imp. s , yb s , imp.

770 990 1625 3330 33. 728 790 1105

960 1340 1380 3280 4. 712 775 828 843 . 1000 1075 1130 1260 1275 1360 1420 1460 1650 3330
~~

Lead metaborate Pb(B0z)n. HzO 1 0 . 3 s, vb 7.45 m 7.2 Nujol? 3.05 m Sodium tetraborate NazBiOi. lOHzO 14.05 w 12.9 w 12.1 s 10.6 s 10.0 s w 9.3 8.85 m 7.95 m 7.85 m 7.35 vs 7.05 vs 6.85 Nujol? 6.05 m 3.0 vs

12. Potassium carbonate KzCOa 865 11.55 m 1 1 . 1 vw 900 6.9 vs 1450 -3220 3.1 m, vb

13. M a nesium carbonate basic 3 M g e O ~Mg(OH)n.3H;O . 1 2 . 5 vw 800 11.7 vw 855 vw 885 11.3 7 . 0 vs 1430 vs 1490 6.7 2.9 111, vb 3450
14. 715 877 1430 1785 2530 Calcium carbonate CaCOa 14.0 w 11.4 s , s p 7 . 0 vs 5.6 vw 3.95 vw

s,sh
vw

Sodium nitrite NaNOz 12.03 8.0 7.5 m, s p

vs

m,sh

Potassium nitrite KNOz 12.05 s , s p 8.1 vs 7 . 5 m, sp 7.25 m 3.9 vw 2.9 vw Silver nitrite AgNOz 12.0 w 11.8 v w vs 8.0 7.25 vs

5.

705 782 833 918 1000 1060 1085 1130 1155 1240 1315 1340 1440 1655 2480 3330 3390 3560
6.

Potassium tetraborate K2BiOi. 5Hn0 14.2 vw 12.8 vw 12.0 s 10.9 s 10.0 s 9.45 vw 9.2 s 8.85 v w 8.65 w 8.05 m 7 . 6 2 sh 7.45 s 6.95 s 6.05 w 4 03 vw 3.03 s 2.95 s 2.81 s Manganese tetraborate MnBiOi.8HzO 10.1 9 . 4 1 s , vb 8.7 7.3 s 6.9 m 6.1 w 2.95 8 Sodium perborate NaBOs.4HzO vw 13 0 w 12 0 11 75 w vw 11 4 TS 10 7 9 8 8 9 3 m 8 5 s 8 05 s 6 05 w vs 3 0
8.

15. Barium carbonate BaCOa 697 1 4 . 3 5 vi 858 11.65 s , s p 6 . 9 5 vs 1440 16. 747 865 1450 -3330 Cobaltous carbonate COCOS 1 3 . 4 vw 11.55 m 6.9 vs 3 . 0 w , vb Lead carbonate PbCOa 14.6 w 1 1 . 9 vw 7.1 YS

1210 1310 1345 2170 3450 25. 1420 1650 2050 2860 3060 3149 26. 758 950 1620 2020 3330 27. 746 945 1630 2020 3400 28. 1630 2060 3500 29. 835 1105 1150 1370 1615 2090 3450

24. Silver cyanate AgOCN 8 . 2 5 vw 7.65 w 7 . 4 3 vw vs 4.6 2.9 vw Ammonium thiocyanate NHiSCN 7.05 s 6 05 m 4 88 s 3.5 m 3.27 s 3.18 s Sodium thiocyanate NaSCN w 13 2 vw, b 10 5 6 18 m 8 4 9 ni 3 0 Potassium thiocyanate KSCN 13.4 m 10.6 vw, vb 6.13 m s 4.9 2.95 m Barium thiocyanate Ba(SCN)z. 2HzO 6.15 m 4 . 8 5 vs, s p 2 . 8 5 vs Mercuric thiocyanate Hg(SCN)z 1 2 . 0 vw 9 . 0 5 vw vw 8.7 s 7.3 w 6.2 4.78 8 2.9 w

17.

38. Barium nitrite Ba(N0n)z. H20 820 1235 1330 1640 3360 3510 39. 830 1340 1390 1630 1740 12.2 8.1 7.53 6.1 2.98 2.85
w vs

685 840 1410

18.

m
m m ,sp

m , SP

Ammonium bicarbonate NHiHCOi 14.25 12.02 10.08 9.7 9.58 7.55 7.15 6.17 6.05 5.3 3.92 3.27 3.17

990 1065 1150 1370 1450 1640 3390

7. 770 833 852 877 934 1020 1075 1175 1240 1655 3330

703 832 993 1030 1045 1325 1400 1620 1655 1890 2550 3060 3160 19. 662 698 838 1000 1035 1050 1295 1410 1460 1630 1660 1900 2040 2320 2500 2940

s
s
s, sp w, SP w , SP vs, b vs, s p

Ammonium nitrate NHiNOa 12.05 w

;:i5} 6.13 w
5.75 w w 2.93 Sodium nitrate* NaNOa 11.96 m , s p 7.36 vs 5.59 v w 4.12 vw Potassium nitrate KNOI 12.14 m, s p 7 . 2 5 vs 5 . 6 6 vw Silver nitrate AgNOa 13.64 vw 12.45 11.98 w vw 7.42 YB

s s

w m
VS,SP

3410 40. 836 1358 1790 2428 41. 824 1380 1767 42. 733 803 835 1348

vs, sp

807 885 1195 1450 3270

Boric acid &BO3 12.4 m vw 11 3 8.37 s,sp 6.9 vs 3.15 s

Sodium bicarbonate NaHCOs 1 5 . 1 5 w (COZ?) 14.35 R 11.95 10.0 9.65 9.55 7.73 7.1 6.85

E} 5.27 m
5

4.9 4.3 4.0 3.4

vw w (COZ?) s. b

3 0 . Lead thiocyanate Pb(SCN)E 2030 4.93 8. sp w 2080 4.8

1256
Table 11.
vw = very weak

ANALYTICAL CHEMISTRY
Positions and Intensities of Infrared Absorption Bands (Continued)
s = strong
vs = very strong

w = weak

m = medium

ah = shoulder

b = broad

vb = very broad

sp = sharp

imp. = impurity

= I<Br region (15-25p) examined

Cm. - 1

RZicrons I 43. Calcium nitrate Ca(N0a)z 820 12.20 w 9.58 vw 1044 s 1350 7 4 1430 7.0 s 6.1 m 1640 s 3450 2.9 44. Strontium nitrate Sr(NOdz

Cm. - 1
54.

Microns I Calcium phosphate, tribasic Caa(P0a)z 10.4 v w 962 1030 9 . 7 ' YS, vb 1085 9.2 3230 3 . 1 m, b

Cm. -1 Microns I 63. Magnesium phosphate, dibasic MgHP04.3H20 882 11.35 m 1020 9.8 s 1055 9.5 s 1160 8 6 8

55.

45. 729 817 1352 1418 1774 2410

Barium nitrate Ba(N0s)t 13.72 6 , SP 12.24 S , S P 7 . 4 0 vs 7.05 m,sp 5 64 w, SP 4.15 b

UT,

Manganese phosphate, tribasic Mns(P0a)z. 7Hz0 935 10.7 vw, sh 980 10.2 w 1020 9.8 s 1040 9.6 ?sh 1070 9.35 s 1145 8.75 w 1250 8.00 w 1300 7.7 w 2470 4.05 vw 3170 3,l5'! 3330 3450

35

Cm.-' hlirrons I 70. Calcium phosphate monobasic, Ca(H2POa)z. ~ 2 0 670 14.9 m, vh 855 w, r b 885 915 10 9 ' v w , sh 950 10 5 s. h 1085 9 2 s,b 1160 8 6 w 1235 8 1 s,b 1640 6.1 m 2320 4.3 m, vb -2980 3.35 s , v b

::::}

71. Calcium phosphate, dibasic CaHPOa. 2H20 880 11.35, m 990 10.1 1050 9.5 1 s, r b 1125 8.9 J 1350 7.4 ? 1650 6.07 m -2270 4.4 m, vb -3000 3.3 m 3610 2.85 v w , sh 64. 697 748 775 833 848 1420 1460 3450 72.

i:: I

56.

836 1378 1587 1790 2431 3170 3360

46. Cupric nitrate Cu(N0a)z. 3Hz0 11.96 w 7.26 vs 6.30 6, SP 5 58 v w 4 . 1 1 vw 3 15 w 2.98 s, b Cobaltous nitrate Co(NOa)2.6HzO 12 4 vw, r b 11 96 w, 6p 7 29 vs 6 1 m 3 1 m , sh 2.93 s Lead nitrate Pb(N0a)z 13.77 u ' 12.39 v w 11.96 w, sp 7.28 w

Nickel(ous) phosphate, tribasic Nia(P0a)~. 7Hz0 735 13.6 w. vb 877 11.4 w Rh 943 io 6. w., .~. 100.5 9.95 s 1060 9 . 4 5 w, sh -1440 ?) 6 . 9 5 w (Sujol 1595 6.27 w -3030 3.3 s 3450 2.9 m,sp

Sodium metaarsenite NaAsO, 14.36 vs, b 13.35 m 12.9 w,ah 12.0 s, sp 11.8 s , s p 7.06 v w 6.85 m, sp 2.90 w , b Calcium orthoarsenate, tribasic Ca,(AsO4)2

65.

Barium phosphate, dibasic BaHPOa

57.

47. 807 836 1372 1640 3230 3410

Copper(icj phosphate, tribasic C~a(POa)2.3Hz0 645 15.5 m 855 11.7 m 925 10.8 s 960 10.4 s 1010 9.9 s 1070 9.35 s 1100 9.1 m , sh 8.75 m 1140 7.75 m 1290 3390 2.95 m 58. Lead phosphate, tribasic Pbs(P0a)z

73. 2440 2700 4.1 3.7

w

66. 900 1080 1275 1420 1440 -1610 -2270 2900 3050

48. 726 807 836 1373

59.

835 1361 1613 1785 2440 3230 50. 816 1325 1380 1640 3390 51.

49. Ferric nitrate Fe(NOa)a,9HzO 11.98 w 7 . 3 6 vs 6.19 m 5.6 vw 4.1 vu. 3 . 1 s , vb Bismuth subnitrate BiONOa. H20 12 27 vw 7.55 s 7.25 vs 6.1 vw 2.95 m, b

Chromic phosphate, tribasic CrPOa. H?O 1030 9.7 vs, vb 1625 6.15 w 3230 3 . 1 E, b Ammonium phosphate, dibasic (NHa)zHPOc

Ammonium phosphate monobasic NHaHzPOa 11.1 w , vb 9.25 m, b 7.85 m 7.05 w, sh 6 . 9 5 rn 6.2 w, vb 4.4 w, vb 3 . 4 5 w, sh 3.28 m

Sodium orthoarsenate, dibasic NazHAsOa.7HzO 712 836 1175 1280 1640 2175 2380 -3130

74.

Lead orthoarsenate, dibasic PbzHAsOc 743 13.45 m , b 800 12.5 vs Potassium orthoarsenate, monobasic KHzAsOa 13.3 11.75 9 8 7.9 6.3 4.4 3.85 m, b m, b vw, b m, vb m ,vb m. vb
m

75. 750 850 1020 1266 1585 -2275 -2740

60.

67.

Sodium phosphate, monobasic NaH2POa. HzO

76. 803 840 1040 77. Sodium phosphate, dibasic NanHPOa. 12HzO 11,55 9 865 1 0 . 4 5 w, sh 958 10.15 S 985 1070 9 . 3 5 17s 1125 8.9 u-, sh 1145 8 . 7 5 vw, sh 1185 8 45 w 126.5 7.9 W 1630 6.13 m -2220 4 . 5 w , vb 3280 3 . 0 5 vs, vb 61. Potassium phosphate monobasic* KHzPOc 538 18 59 m 900 1 1 . 1 m, vb 1090 9.15 m , b 1300 7.7 m 1640 6 1 m, b 2320 4.3 m, b 68. 690 740 950

Sodium phosphate, tribasic NaaPOa. 12H20 694 1 4 . 4 real? 1000 1 0 . 0 vs 6.9 vw 1450 6.03 m 1660 3200 3.13 vs, b Potassium phosphate, tribasic KaPOi 10.0 vs, vh 1000 6 . 3 w , vb 1590 3180 3.15 vs, b

1640 2850 2820

6.1

m , vb

4 . 2 5 s, b 3.55 s , b

Arsenic trioxide AS?Oa 1 2 . 4 5 vs 11.9 w, sh 9 6 vw, b Antimony trioxide Sb2Oa 14.5 w 1 8 . 5 vs 1 0 . 5 vw, b

52.

53. Magnesium phosphate, tribasic Mga(POajz.4HzO 768 13.05 w, b 887 1 1 . 3 vw, b

1% 1040

78. Antimon pentoxide Sbr8r 685 1 4 . 6 v w , real? 740 13.5 s , v b 3225 3.1 w, b
79. Ammonium sulfite (NHa)zSOa. H20 9 . 0 5 vs, b 7 . 0 8 v s , sp 3.25 s Sodium sulfite Na2S03 10.4 rs,b 11.35 w 8 2 vw

62.

%E5]

,"
m
w,sh w

1135 1155 1230 1640 3260 3460

8.83 8.65 8.13 6.1 3.07 2.9

m
s m, s h

Potassium phosphate, dibasic KzHPOc 837 11.95 s 934 10.7 s 990 1 0 . 1 vs, vb 1110 9.0 w,sh 1350 7.4 m, sp 1835 5.45 m 2380 4.2 m 2860 3.5 m

69.

iii:

Magnesium phosphate, monobasic Mg(H2POa)z 755 13.2 w. vb 943 10.6 1040 9.6 m,vb 1150 8.7 J 1235 8.1 w , sh 1640 6.1 m

1105 1410 3075

80.

s. b

960 1135 1215

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2
Table 11. Positions and Intensities of Infrared Absorption Bands (Continued)
vw
=

1257

very x e a k Nicrons

xv = weak

m = medium

s = strong

YS =

= KBr region (15-25p) examined

very strong

sh = shoulder Cm. -1 101.

b = broad

vb = very broad

sp = sharp

imp. = impurity

Cni.-'

Cm. -1

Microns

Rlicrons

Cm. -1

Microns

81. Potassium sulfite K?SOS. 2H20 913 10.6 vs, vb 1100 9.1 vs, b 1175 8.5 s 6.07 v w 1645 5.3 vw. 1885 2.95 m 3390
82.

Calcium sulfite CaSOs. 2HzO

92. Copper sulfate cusoa 680 14.7 m 805 12.45 m 860 11.6 m 1020 9.8 w, sp 1090 9 . 2 vs, vb 1200 8.35 s 1600 6.25 w, sh -3300 3.15 s , b

665 1000 1115 1645 2250 3200 3360 3450

102.

Magnesium thiosulfate MgSzOr .6Hz0 -1n.O s 10.0 s 8.95 vs 6.08 m 4 . 4 5 > v. vb 3.13 2.981 s 2.9 ) Barium thiosulfate BaSzOs.U2O

:$; i:::
653 1100 1210 1625 3400

15.3

9.1 8.3 vw 6.15 m,sp 2.94 s , s p

m, b ~ sh , vw,vb

93.

627 650 720 770 920 1030

1080

83. Barium sul5te BaSOa 638 15.7 m 917 10.9 vs. b 990 10.1 w 1070 9.35 m,vb 1200 8.35 m 1410 7.1 v w 84. Zinc sulfite ZnSOs.2HzO 11.7 s , vb 10.57 w 9.8 s 9.1 m 8.6 m 6.13 m 3.15 2.951

1630 1650 3195

94.

Zirconium sulfate* ZrSOa. 4Hz0 15 95 w 15.4 w 13.8 w 13 0 v w , sh 10 9 v n , sh 9 7 w, sp 9.25 vs, vb 6.12 m 6.05 m 3.13 s

110. Sodium selenate Na~Se04.10H~O 735 13.6 vw, sh 793 12.6 vs 838 11.95 vs 573 11.45 vs I105 9 05 m 1125 8.9 m, s p 8.6 w 1165 1240 8.07 m 1390 7.2 s 1640 6.1 m 2350 4.25 s 3220 3.1 m 3500 2.85 s , s p
111.

810 824
875 857
89?

Potassium selenate KsSeOa 12.35 v w . s h 12.13 s , sp

Chromium potassium sulfate Crz(SO4)d . KzSOa. 24Hz0 1090 9.2 vs 1660 6.05 w, b 2.97 m 3370

103.
4.56

Sodium metabisulfite* Na&Os

21.91 14..58

.: I2 a31
660 f i f i 7 973

m
vs
1's
vs

1080 1110 1140 1375 1745 2390

112.

11.67 11.42 11.15 9.22 9.0 8.75 7.28 5.73 4.18

vw m vw
vw vw

vs w, sp
w,8p

855 945 1020 1100 1160 1630 3170 3390

95. Ammonium bisulfate NHaHSOa 855 11.7 m. b 1035 9.65 m, b 1180 8.5 m, b 1410 7.1 vw 3180 3.15 m

18.81 m 1.5. 171

1,j.n /

lofin

11x0
104.

1265

in.25 0.4.5 8. .5 7.9

Copper selenate CuSeOa. 5Hz0

v w , sh

, Ammonium sulfate 85. (NHa)zSOa 15.5 w 645 9.05 vs. b 1105 1410 7.1 vs, sp 5 , 7 5 vw 1740 3.25\ 3032 3.161 s * s p 3165

96. Sodium bisulfate NaHSOh 655 215.3 ni 12.95 vw 773

Potassium metabisulfite KZSZO5 RR2 1,5.l rn 475 1 0 . 2 5 cs iofin 4.ii 10x0 9 . 2 i ni

1105

770 858 922 1600 3220 3390

113.

13.0 m, b 11.65 s 10.85 m 6.25 m , s p 3.1 \ 2.951

Sodium chlorate NaClOa 10.7 s , s p 10.35: 10.1 ( vs Potassium chlorate KClOa 10.65 w

117.5 1250
8.0 8.1 6.02 3.85 2.88
97. m s m vw m

9 0.5 R. i

ni
7's

8.0 r w , ~ h
Ammonium persulfate (NHi)zSzOq 15.7 vw 14.23 s 12.5- w 11 ..?.a 7-w

935 965 990

114.

105.
fi?7

86. Lithium sulfate* LizSOa. H z 0 15.77 m 634 815 12.25 v w , real? 1020 9.8 v w 1110 9.0 T S 1170 8.55 m, sh 1 1380 7.25 Nujol 1625 6.15 m , sp 2.88 m 3470

702

793

87. Sodium sulfate NazSOa 645 15 5 w 1110 9.0 vs

88. Potassium sulfate* KzSOa 1110 9 0 vs 89. Calcium sulfate CaSOa. 2Hz0

820 848 877 1005 1065 1160 1280 1325 1640 2600 2900

Potassium bisulfate KHSOa 12.2 w , s h 11 8 s 11.4 s 9.95 5 9.37 S , SP

865

938 962

10.4

YS

lOR0
1085

-1190 1280 14211 3260

4.45 4.23 8.4 7.8 7.0.5

s,sp

m,
v'

SD

w,sh

115. Barium chlorate Ba(ClOa)n.H z O

3.07

t:;:5]
1610 3S40 3570
116.

8.6

vs,b

7.78 s 7.55 w, s h 6.1 w m. vb 3.85 v w 3.45 s , v b

106. Potassium persulfate

KzS201

vs. v b 6.2 m,s p 2.83 s , s p 2.80 s , s p

710
I060

14.1
9 1?

2:: j>

1270
1100

78 8
7 7

s , 3p

3300
107. 720
788

3 02 w

vs

667 1010 1130 1630 1670 2200 3410

90,

14.95 s 9.9 w, sh
8.85

6.13 5,95 4.55 2.93

vs, vb s. sp w m. b s, b

98. Ammonium thiosulfate (NHdzSzOa 953 10.5 s 1065 8.4 s 1390 t.18 s 1650 6.05 w 2960 3.4 s , vb 99. Sodium thiosulfate Na&03.5H20 677 14.8 s 757 13.2 v w , sh 1000 10.0 vs 1125 8.9 8.6 1165 1630 G,l5 w 1660 6.03 m

112.5 1450 3330

Sodium selenite NazSeOa 18.7 vs 12.7 s 8.4 w , h 6.9 Nuiol ? 3.0 w, b

1060 1136 1420 3330

Ammonium perchlorate NHaClOa 9.45 v s 8.8 s , s h 7.05 s 3.0 s, sp

1 1 7 . Sodium perchlorate
1100 1630 2030 3570
NaCIOI. HzO 0.1 vs, b 6.14 s , s p 4.93 vw 2.80 s , sp

660 825
1025 1135 3225

Manganese sulfate MnSOd.2HpO 15.15 m 12.1 s 9.78 nr

8.8

) '"

108. Copper selenite CuSe08.2Hz0 714 14.0 v s 768 17.0 m.sh 807 12.4 r w , s h 918 10.9 m 1570 6.35 m 1650 6.05 w 4.4 vw, v b 2270 -3120 3.2 1 3450 2.9 1

118. Potassium perchlorate KClOc w 637 15.7 940 10.65 v w 1075 93 s 1140 8 . 7 5 s . SI1 1990 5,02 cw

3.1

vs, vb s, b

2080 3390

2.95 vs

109.

91. Ferrous sulfate*

611 990 1090 1150 1625 3330
FeSOh. 7Hz0 16.37 s , v b 10.1 vw 9.2 vs, vb 8.7 m,sh 6.15 m 3.0 s , b

1 0 0 . Potassium thiosulfate KzSzOs. H20 658 15.2 676 14.8 1 00 3 s 995 1120 8 95 v s 1625 6 15 v w 3300 3 03 w

770

Ammonium selenate (NH4)zSeOa 13.0 \

@
860 1235 1420 1640 2320 -3140

i:;i31

vs,vb

11.63,' 8.1 w 7.03 s 6.1 m 1.3 ni 3.18 v s

119. Magnesium perchlorate MgClOi 652 15.35 rn 10.58 w 943 10.4 w 962 9.45 vs 1060 8 . 85 \ I 1130 6.13 s , sp 1625 4.8 P , vb 2100 2.83 s 3540

1258

ANALYTICAL CHEMISTRY
Table 11. Positions and Intensities of Infrared Absorption Bands (ConcEuded)

vw

very weak

= weak

m = medium

s = strong

vs

= very = KBr

strong s h = shoulder b = broad region (15-25p) examined

vb

very broad

sp = sharp

imp. = impurity

C m - 1 Microns I 120. Sodium bromate NaBrOz 807 1 2 . 4 vs

121. 790 Potassium bromate KBrOa 12.65 vs Silver bromate AgBrOs 13.08 s 12.55 vs 7 . 2 5 Nujol ?

Cm.-1 Microns Z 132. M a nesium chromate MgErO4.7HzO 695 14.4 w, v b 765 1 3 . 1 w, b 855 11.7 m , s h 877 1 1 . 4 vs 1620 1650 ::I%} 2270 4.4 m, b 3260 3 . 0 7 vs, b

Cm.-1 Microns I 140. Calcium dichromate CaCrzO7.3HzO 725 1 3 . 8 vu. 830 12.05 m 900 11.1 m 940 10.65 s 1625 6.15 m 3450 2.9 s 141. Copper dichromate CuCrz01.2HzO 1 3 . 3 s , vb 10.65 s 6.15 m 2.9 s Sodium molybdate NazMoO,. 2 H ~ 0 12.2 vs 11.7 m 11.1 m , s p 5.95 w 3.05 s Potassium molybdate KzMoOa.5HzO 1 2 . 1 va 11.1 m 3.02 m

Cm.-1 Microns I 151. Barium permanganate Ba(Mn0a)t 840 11.9 m , s p 877 11.4 s 913 10.95 s 935 10.7 m 152. Sodium ferroc anide NaaFe(CN)s. lOd0 1625 6.15 s , s p 2000 5.0 vs 2020 4.95 m, sh

122. 765 797 1280 123.

133.

Barium chromate BaCrOa 10.75 s , s h 2.9 w

i i g ii:z5} vs b
930 3450 134. Zinc chromate ZnCr04.7HzO 720 13.9 m 795 12.55 s 875 11.4 940 10.65 1050 9.5 1090 9,l5 s,b 1183 8.45 m 1620 6 . 1 5 vw 1820 5.5 vw, b 2700 3.7 w, b 3450 2.9 s,b

750 940 1625 3450 142. 820 855 900 1680 3280 143. 825 900 3310 144.

; ; ; i;:?}
800 124. 738 755 800 12.5

Sodium iodate NaIOs

vs

153. 930 995 1630 1650 2015 3410 3510

Potassium iodate KIO? 13.55 vs 13.25 s 12.5 w

Potassium ferrocyanide &Fe (CN)8.3H20 10.75 vw 10.05 vw 6.13 8 , sp 6.07 m 4 . 9 6 vs

;:%}

125. Calcium iodate Ca(I0s)z. 6HzO 13.35 m 748 13.15 m 760 775 12.9 s 817 12.25 8 827 1 2 . 1 vw, sh 838 11.93 v w , s h 1610 6.20 w , s p 3350 3450

i::8}

135. Lead chromate PbCrO4 825 855 vw. vb 885 11.3

::::1

Ammonium heptamolybdate (NHa)nMoiOzi.4HzO 663 1 5 . 1 vs 836 11.95 m 877 11.4 vs 913 10.95 w , s h 1420 7.05 s 1640 6.1 w 3080 3.25 s, b 145. 810 822 925 1670 3310
8.50

Calcium ferrocyanide CazFe(CN)n. 12Hz0 1615 6 18 m 2015 4 . 9 6 vs, sp 3390 2 . 9 5 vs, b

154.

155. Potassium ferricyanide KsFe(CN)e 2100 4.77 s

126. 848

Potassium periodate KIOa 1 1 . 8 vs

156. 136. 745 950 1010 1300 1625 3460 3520 Aluminum chromate Alr(CrO4)s 13.4 s , v b 10.5 s , b 9.9 s 7 . 7 vw 6.15 m Sodium tungstate NazW04.2 H z 0 12.35 w , s h 12.15) 11,751 vss 10.8 w 6.0 w 3.02 s 847 1333 1430 1575 1645 2665 2780 3450

127. Ammonium metavanadate NHdVOa 690 14.5 s, vb 843 11.85 s 888 11.25 s 935 10.7 s 1415 7.08 s , sp 3200 3.12 8 , sp 128. 693 828 910 935 957 3450 129. 74 5 843 865 935 1410 1650 2860 2990 3120
130.

;:ii}

Sodium cobaltinitrite NaaCo(N0l)s 11.8 s , s p 7.5 vs 7.0 vs 6.35 m 6.07 w 3 . 7 5 vw,s p 3.6 vw, sp 2.9 m

Sodium metavanadate NaVOa . 4 & 0 1 4 . 4 s, b 12.08 s 1 1 . 0 vw 10.7 10.45} 2.9 w, b Ammonium chromate (NHd)zCrO4 13.4 m 11.85 m, ah 11.55 vs, b 1 0 . 7 m. sh 7.1 8 6.05 m 3.5 m.sh 3.35 s 3.2 m,sh Sodium chromate NaKrOd 14.7 m

137. Ammonium dichromate (NH4zCrzOi 730 1 3 . 7 vs 877 11.4 m 900 11.1 m 925 10.8 s , s h 950 10.55 s 1410 7.1 s,sp 2850 3.5 m, sh 3060 3170

146. Potassium tungstate KsWOc 750 13.3 vw 823 1 2 . 1 5 vs, b 925 10.8 w 1680 5.95 w 3170 3.15 m 3320 3.01 w,sh
147.

157.

::%}

794 1640 3390 148.

Calcium tungstate Caw04 1 2 . 6 vs, vh 6.1 w 2.95 m

Ammonium hexanitratocerate (NHdzCe(N0dn 745 13 42 8 , sp 803 12 45 m, sh 807 12.4 8 , sp 815 12 25 vw 1030 9 7 s, s p 1050 9 5 vw 1260 7 95 vs 1325 7 55 w 1420 7 05 s 1530 6 6 vs, b 3210 3 11 s, b 158. Ammonium chloride* NHiCl 7.1 8 , sp 5.75 w,b 5.0 vw 3.5 m

138.

680 820 855 890 915 1665 2125 3170 131. 858 935

i?:: 11.2

Sodium dichromate NalCrzOr .2Hz0 13.55 vs 12.8 m 11.25 8. sp 11.0 m , s p 9 . 0 7 vs 7.2 Nujol 1 8 , SP 2.85 8

;:A;}

Sodium permanganate NaMn04.3Hz0 840 1 1 . 9 vw, sh 896 11.15 vs 1625 6.15 s,sp w,b 3510 2.85 s

$ : : : ::e}
149.

1410 1780 2000 2860 3070 3150

::?!}

vs, b
m,sh s,sp m, b 139. 568 760 795 885 905 920 940 1305 Potassium dichromate* KnCrzOi 17.61 w 13.15 vs 12.55 m 11.3 m, SP 11.05 m , s p 10.85 w , ~ h 10.65 vs, b 7 . 6 5 vw

10.90 6.0 4.7 3.15

Potassium permanganate KMnOd 845 11.85 w 900 11.1 vs 1725 5.8 w 150. Calcium permanganate Ca(Mn03z.4HzO 11.9 m 11.05 vs, b 6.15 8 , s p 2 . 8 8 vs

159. Barium chloride BaClz.2HzO 700 1 4 . 3 vs, vb 1615 6.18 8 , sp 1645 6.07 8,sp 3370 2 . 9 7 vs 160. Nujol 3.427 s 3.495 a 6.859 m 7.257 m 13.89 w

vs.b

Potassium chromate KzCrOh 11.65 w, sh 11.45 vs 10.7 s

840 905 1625 3470

2918 2861 1458 1378 720

V O L U M E 2 4 , NO. 8, A U G U S T 1 9 5 2

1259

one of the salt plates with a very thin layer of solid paraffin to The purities of the samples are indicated in the legends for the hold the particles in place (6, 7 ) . The fine powder may be precurves. pared by grinding, by evaporation of a suitable solvent (6, 7 ) , or Some idiosyncrasies of the curves warrant mention. Many of by sedimentation ( 5 ) . Vacuum evaporation which has been them show weak remnants of the carbon dioxide bands near 4.3 used for preparing films of ammonium halides ( I I ) , may be useful and 14.8 microns. The latter always appears as a sharp upward for other relatively volatile inorganic materials. pip. Many of the curves exhibit a drop in transmission near Spectroscopic Procedures. 8 1 1 samples were examined from 15 microns and then a small increase beginning at 15.5 microns. 2 to 16 microns with a Baird XIodel A infrared spectrophotometer. The initial decrease is due to the absorption by the sodium chloride Wave lengths are accurate to about zt0.03 micron, although for plates, which was not compensated in the reference beam. The broad bands the error of judging the center may exceed this. It reason for the later increase is not known, but it is not real. It was sometimes found that duplicate spectra for the same comhas the effect of suggesting an incorrect position for bands near pound differed by more than this amount. Some oossible reasons are mentioned below. Table 111. Infrared Bands of Various Nitrates (Cm.Representative ex a m p 1 es of Intensity m, s p a w m, sp w VS S S VS vw several ions were examined in .. , . 836 .. 1358 .. .. 1790 2428 the potassium bromide region 824 1767 .. 1380 , . .. 733 803 835 1318 .. with a Perkin-Elmer 12B spec, . .. 820 1044 (1359) ( 1430) (lii0, 737 .. 815 .. 1387 1795 1441 .. 2iio trometer. Likewise, a series of 729 .. 817 .. 1352 1418 1774 (2410) ten nitrates was examined in the (1785) .. 835 .. 1361 , . . . (1640) i6ij .. (807) 836 ., 1372 .. rock salt region with this same 836 .. 1378 .... 1587 1790 2431 726 807 836 .. 1373 , . .. instrument in order to fix the Bands >3000 cm.-L are omitted. wave lengths of absorption more ( ) Baird values, less accurate. accurately. a w, ni, s = weak, medium, strong. g p = sharp. v = very. No attempt was made to put the spectra on a quantitative basis. RESULTS 16 microns. For example, in ferrous sulfate heptahydrate The spectra are presented a t the end of this paper. Table I ( S o . 91) the curve indicates a band a t 650 cm.-l (15.5 microns), lists the compounds examined and gives the numbers of the corbut actually it is a t 611 ern.-' (16.5 microns). responding spectral curves. Table I1 summarizes the positions DISCUSSION OF RESULTS of the bands in wave numbers and in microns, and gives estimated peak intensities. If more precise wave numbers have been The spectra range in quality from surprisingly good ones, with determined with the Perkin Elmer spectrometer, they are used. sharp, intense bands (see curves for barium thiocyanate dihyAsterisks indicate those compounds examined in the potassium drate, No. 28; strontium nitrate, No. 44; and ammonium bromide region. hexanitratocerate, No. 157,) to very poorly defined ones such as The spectra themselves are shown in graphical form. Nujol those for potassium silicate, S o . 32; monobasic magnesium bands are marked with asterisks; portions of curves run in fluorophosphate, No. 69; and monobasic potassium orthoarsenate, lube are indicated by an F. The spectra of Nujol and fluorolube KO.75. I t seems to be characteristic of the phosphates, and are included for comparison (No. 160). I n a few cases the ponder especially of their monobasic and dibasic modifications, to have was used without a mulling agent; these are indicated by P. ill-defined spectra. The reason for this is not clear, but it may be due to lack of a single, well-ordered crystal c rn-1 structure. Effect of Varying Positive Ion. One of the purposes of this study was to ascertain whether the various ions have useful characteristic frequencies. It was therefore of interest to know the effect of altering the positive ion. The spectra of ten SUIfates are shown in Figure 1 in the form of a line graph. I t is seen that two characteristic frequencies occur, one a t 610 to 680 em.-' ( m ) and the other a t 1080 to 1130 cm.-l (s). There is enough variation between the individual sulfates so that it is often possible to distinguish between them from the exact positions of the bands. Table I11 presents similar data for ten nitrates. Again there are characteristic frequencies, a t 815 t o 840 cm.-' (m) and 1350 to 1380 (vs). The authors I have been unable to find any orderly relation between the positions of these nitrate bands and a MnSO4.2W property of the positive ion, such as its charge or I I mass. This is not surprising, for there are a t least ZrSO4.4W three reasons why a frequency may shift slightly as I I1 . I C r S 04' K2S 04 the kind of positive ion is changed.
24 W

Figure 1.

Comparison of Infrared Spectra of Ten Sulfates

W. Water vh. Very broad s h . Shoulder

The different charges and radii of the various positive ions produce different electrical fields in the various salts. These doubtless affect the vibrational frequencies of the negative ions. (Continued on page 1298)

1260
IW

ANALYTICAL CHEMISTRY

10

/4n
I

= bo
z
40

F
i
f~

A~
~

I
~

Sodium metaborste, NaBOz

C.P.

20
~

,
I

J
8

~ I
7

0
2
4

Z ; \$ U :
~

\
I

;I

5 6 I WAVE LENGlH IN MICRONS

10

I1

12

I1

I4

1s

' 0

500)

Urn

low

2SW

WAVE NUMBER5 IN CM' ,5WI,W ?OW

IIW

I200

liW

Iwo

WAVE NUMBERS IN CMI 9w

aw

700

b2S

Magnesium metaborate, Mg(BOz)z.SH:O

C.P.

5 b 7 WAVE LENGTH IN MICRONS

WAVE NUMBERS IN CM

IO

11

12 I1 WAVE LENGTH IN MICRONS

WAVE NUMBERS IN CM' I00

I4

IS

I6

5wo
lM

Urn

100)

2100

lwa

Ism

,104

I1W

I100

IIW

Iwo

9w

7w

b2S 100

Lead metaborate, Pb(BOdn.Hz0

IO

IO

C.P
560 bO

g*
20

40

20

5 6 7 WAVE LENGTH I H MICRONS

IO

I,

I1 I1 WAVE LENGTH IN MICRONS

I4

IS

I6

Sodium tetraborate, Na2BO. 10Hz0

C.P.

WAVE LENGTH IN MICRONS

WAVE LENGTH IN MICRONS WAVE NUMBERS IN CM1

WAVE NUMIRS IN C H
500)
(ooo

100)

2Mo

low

,5Wl,W

1100

IIW

llW

Iwa

9W

ud

7w

625

IM

Potassium tetraborate KgBdO?.5HzO c

P.

IO

i z*
z

1"

20

0
WAVE LENGTH IH MICRONS WAVE LENGlH

I H

MlCRMlS

V O L U M E 2 4 , NO. 8, A U G U S T 1 9 5 2
IW

1261
Manganese tptraborate, MuB4&.8HzO
C . P .
M)

80

I I

"

6'*
10

i ZbQ
z

f, ' 0 .

L'

I!
II

j
~

Y
20

v
I
4 5

'
b

I
I
10

1
1

ilo
0

0'

II

1 1

I1

I4

I5

I .

IW.

'I
Y

Sodium perborate, '1'" ?;aBOa.lHdI

10

s5
j
r

V "

IO

60/

E'O

IO

la/ ! \l/* 1

\AIL
I
1
7
I

I
~

l h / ,
I

C.P.
(0

I
~

11

:L/;
1
~

I
I
I

*
10

I
6

I
I1

l
I I1

l
0
I1
I4

10

I5

Ib

Boric acid, HiBO

02.

SVX 100.

4oW

1VX

ZSW

1VX

IO

<

r
F !

z p7f
c L
~

'
1

IIW l u x )

1100

IlW

liW

loo0

9w

1 0 )

7m

615 loo

uI
I

*
I

9
m
M

Boron nitride, B N

' *
10
J

Pure

c
Y

'Ob

I
10

I
Y

.
~

I
5

1
b

Q'

I I
7 I
9

100.'

# 10.

10

11

I1

I4

I5

Ib

I5W

lux)

1lW

1100

1100

IVX

(w

iw

700

615

1'0

Lithium carbonate, LizCOa

H
fa-

i *1

zi

i
I \,
~

IO

u
64

AR

40

lo

0
9

I1

I1

IS

Ib

1262
WAYL NUM?ERS IN C M '

ANALYTICAL CHEMISTRY
5ccO
wO 3w0

15W

lw(.

1 5 w 1 4 c a 1100

iico

)loo

iom

WAVE hLM5ERS Ih C U I
FCO 6CC

100

bli

Sodium carbonate,

NazCOi
AR

Potassium carbonate, KnCOi

AR

Magnesium carbonate, basic, 3MgC.01Mg(OH)n.aHnO Unk

Calcium carbonate, CaCOa AR

5wO

u40

1wO

2 m

1004

ISWilW

IIW

I700

ll00

IOW

9w

IM

IW

b15

IW

I
7
I

15Im Barium carbonate.

! -80

BaCO:

80

AR

f 5.

"
I
~

1"
Y
10

~ -

10
I

1-1

b
1

41

WAVE LENGTH IN MICRONS

I1 WAVE LENGTH IN W C R M I S

I 1

10

I5

b0

V O L U M E 2 4 , NO. 8, A U G U S T 1 9 5 2
WAVE NUMBERS IN C M '

I,263
WAVE NUMlfRS IN u ( l

5 io0

Cobaltous carbonate, COCOl Unk.

m
0

5 b I WAVE LENGW IN MICRONS

11

I1 I1 WAVf LfNOTH IN MICRONS

14

16

lb

Lead carbonate, PbCOj

Unk.

Ammonium bicarbonate NHiHCOa

Sodium bicarbonate, NaHCOa

C.P.

Potassium bicarbonate, KHCOI

C.P.

1264
IW

ANALYTICAL CHEMISTRY
I

I
80

Sodium cyanide,

NaCN
I

'Na,CO.

k.

NaaCO3
W

impuritg

40

P
20 20

Potassium
cyanide

KCN
IlHCOa and K:COa impurities

Potassium cyanate, KOCN Considerable KHCO impurity

Silver cyanate, AgOCN "Higheat purity '

IW1
IO

\
I

2
c

fM
10

mPY- I,/
-7
I

'

Ammonium thiocyanate,
2 5 1 m

NHaSCN
AR

80

"
F

'D

E"

10

1
1

1
I
8

10

'

10

WAVE LENGTH IN' MICRONS

II I1 WAVE LENGTH IN MICRONS

14

0
5 Ib

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2
Sodium thiocyanate, SaECS

1265

Potassium thiocyanate KBCS AR

WAVE NUMBERS IN C M '

XCC IW

Urn

3wO

1SW

3000

ISW

I4W

IIW

12w

I W

Iwo

9w

WAVE NUMIIERS IN CM 8W

IW

b25
100

Barium t h ~ o c y a n a t e Ba(SCX):.2HzO
C.P.

IO

(0

f e

(0

5" $
10
0 1

20

5 h 7 WAVE UN6TH IN MICRONS

WAVE NUMBERS IN CM 2000

IO

I!

I2 I3 WAVf LENGTH IN MICRONS

I4

lb

sox 4ccc
lW

3mo

25w

I5W

l4W

l3W

17W

IWO

Vw

WAVE NUMOERS IN CM1 8W

703

bl5 lW

1(0

Mercuric thiocyanate, Hg(SCS)*

Pure
(0

I"
Y
20

10

5 6 7 WAVE ttNGrn IN M~CRONS

It I3 WAS W l l i IN MICRONS
WAVE NUMBERS IN C M ' SOD

I4

15

Ih

S W O

4wO

IWO

ISW

WAVE NUUBERS IN C M ' lD00 1503

I+W

IIW

I1W

lax,

9w

7w

hl5

0 1

lop

Lead thiocyanate Pb(SCN)*

C . P .

IO

kt4
n

3
<

rm
v
20
0
1

4Q

5 L 7 WAVE LENGTH IN MICRONS

IO

I1

I1 1 1 WAVE LEN6TH IN MICRONS

Ib

IS

Ib

1266

ANALYTICAL CHEMISTRY
Sodium metssilicate, NarSiOr5HaO
O.P.

Potassium nietrtsilicate, KrSiOi

O . P .

Xm IW

u*yI

1800

1100

lOm

Iyo

100

110)

Irn

Ilm

la4

no

800

1W

(11

Io.

1
8 s"
20
0

7
3

rr-"---/ *
I

\
1
L

33
w

Sodium ~ i l i r o f l ~ ~ o r i d ~ ,

SazSiFe

a.p.

? -

I'
*
I
I

1
~

44

20

I1

ll

I+

I&

Ib

WAVE NUMBERS IN

CM

WAVE NUMBERS IN CMI

Silica gel, SiOmHrO

WAVE LM6W IN MICRONS

WAVE U N 6 W IN MICRONS

5 IW

Sodirim nitrite, NaNOi

H

C.P.

44

10

5
WAVE

LWOM IN HICRM

II

WAbl IuN6W IN I MCRONS 3

It

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2

1267

Potassium nitrite, KXO,

C.P.

tm

'
MI

-.

37IW Mver nitrite, AgKOz

Y

w
C.P.
Y

1I I
20

f
*

I
~

la
20

I
2

fi

1
4

0
5 6 7 WAVE LEWTH IN UlCRONS

IO

1 2 WAVE LENGTH IN WCRONS

14

I5

Ib

WAVI NUMBERS IN C U I

WAVE NUMBERS IN CM I

Barium nitrite, Ba(N0:hHsO

80

C.P.
Y

20

5 6 WAVE LLNGTP IH H U M S

0
IO

II

WAVE ENOW IN

I2

I1

mcRoNs

I4

I5

Ib

im

Animonium nitrate, NHaKOs

W

C.P

20

5 WAVE UNOIH

7 MICROHS

IO

II

12 I> WAVE LENOM IH MICRONS

WAVE HUMBEIS IH C W

I4

Ib

WAVE NUMBERS IN C U

Sodium nitrate, KaNOa

AR

a
WAVf YHCM IN MICRONS

1268
5wO W

ANALYTICAL CHEMISTRY
UDO
105)

2SW

2mO

1100 l4M

llm

IlW

ll00

IXd

rn

im

700,

b25
loo

60

1'

//
1 1

l P \ w d '4 l Io
M

Potassium nitrate, KSOa

I
I
bo/
'

A 11

; g
S

401

*
I

10

I
b

I
7 I
0

10

10

0
1

IS

Ib

Silver nitrate, AgSCs

C.P.

Calcium nitrate.
Ca(Pi0dp
C.P

Strontium nitrate, Sr(XOd3 Unk.

WAVE WUMlERS

N CM

5 100

Barium nitrate, B~.:(?jod?

A It

(D

10

10

5 b 7 WAVE LENbTH H MICRON5

10

It

I1 I1 WAVE LEN6lV IH MICRMIS

16

IC

1b

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2

1269

Cuprio nitrate, Cu(XOi):.3H:O

C.P.

Cobaltous nitrate, CO(;203) 2.6 I20

AR

Lead nitrate, Pb(XO3)

AR

100.

IW

Ferric nitrate,

80

z 2

3bo-

Fe(S03)3.9H20 * 7 4 9 " - '

~

i'

no

i9
20

\r'
'

\ /
~

I
p ,

AR
z i t 4

4a

"

20

W A d LENGTH IH' MICRONS

I
V

2 I3 WAVE LENGTH IN MURCUS

0
Ik
I5

Ib

Bismuth subnitrate. BiOSO3.HnO

Unk.

1270
IW

ANALYTICAL CHEMISTRY

80

EM
f Y
'0

I
\J
I /

\
I

"

1
I

51:
b4

Eodium phosphate, tribasic, NalP04.12H;O

AR

!
1

1
I

\ I
v
D

( 1

i
I

I'\

1
4a
20

10

I
I 1

1
I4 IS

0 Ib

0~ 2

I b 7 W A M L W l H IN MICRONS

I2 I1 WAVE LENGTH IN WCROHS

5 M Mo( I w - ' I (

" '

3oW

,2 'W '

'

I
80

1
\ I

3- ji !
I

*
*

,
I

;
!

i 52lw
I
10

Potassium phosphate. tribasic, &PO4

c. P

/I

a-

lol
0

L: j
~

\\
I

:1*
I
5

I
b

IC/
\

40

I20

I
8

i
I
' 0
I1 I*

IO

11

I2

15

swo k4f8
IW

'

" .

1 m

!'

2100

zoo0

Ism

lua

IlW

I2W

IlW

Imo
I

(00

aw

700

b25

80

?I
f

P g, g

:i I I
I !
10

b-,*
'A -$

I
J

/ . . ,
I

I
I

153r
I8O

Magnesium phosphate, tribasic, Mga(POdyAHz0

C.P.

i?
,

b a

Z"

I; I
*
V
2

t
! I
5 b WAVE LEN6TH IN MlCRMiS

~1
I
I

4a

I
IO

I
I
8

0
0

I1

I2 I3 WAVE LENOW IN MICRONS

Ib

Calcium phosphate, tribasic, Cas(PO4)r

r.e

Manganese phosphate, tribasic, Mni(POdp.7H10

C.P.

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2
Imp

1271
WAVf NUMBERS IN CM1
iim

WAVE NUMltRS IN C M '

tmo

2100

Ima

IW

I-

IIW

IZW

imp

tW

IN I

IW

I
,

I
! I

/ ir\ 7 1 . m . ,
,

qoo
LIS

/ *

Nickel (ow) phosphate, tribasic, Nia(POdz.7 H?O

*
I

,
1
/ ,

I
I
I

i
~

i
l
I

7
I ;

I
I

\ \,
I

L ,

I
0

Copper(ic) phosphate, tribasic, Cut(POa)z.3H10

C P

5wO

IWP

ION

25W

WAYZ NUMBfRS ZOW

H CM
15w Iuc
1100

L m ,

lIW

Iwo

WAVE NUMBERS IN C M ' 9w

IN

100

b15

phosphate, tribasio, 58Iw Lead PbdPOdz

I
IO

C.P.

I?

I
I
~

i*
10

'

I
5 b 7 WAVE LENGTH IN MICRONS I V

12 I1 WAVf LENGTH IN HhROlll

0
I4

I5

Ib

WAVE NUMBERS IN CM

5
iw

Chromic phosphate, tribasic,

(0

CrPOc.Hn0
P.P.

40

20

5 b I WAVf LfNGTH IN UICROM

IO

I1

I1 I> WAVf LENGTH IN MKRONS

0
I4
I6

Ammonium phosphate,

dibaaio,

(NHOrHPOt
C.P

1272
WAW W
100

A N A L Y T I C A L CHEMISTRY
W S IN CUl5a

IUD

I1rn

I200

llrn

Im,

WAVE NUMDERS IN C U I

100

700

b25

100

Sodium phosphate, dibasic, NaSHPO 1.12 H 2 0

S 80

C . P .
U

I"
n I
I 1 4

10

I
8

5 b 1 WAVr W T H IN UCRONS

IW

I
10

I
I1

I
I4

I
I5
Ib

I2 I1 WAVr LW6W IN MICRONS

Potassium phosphate, dibasic, K ~ I I P C I

(0

C.P.
E M

o4
20

WAYS W T H IN MKRONS

WAVE ENSW IN UCRCUS

llagnesium phosphate, dibasic, MgHPOa.3HzO

C.P

w urn Irn

1 m

2x0

WAVE NUMBERS IN C U I

2wo

WAYS NUMBERS IN CU I

5
ID3

Calcium phosphate, dibasic. CaHP04.2H20

C.P

10

m
Lo

jM f
5"

10

20

0
2

5 6 I WAVE UNSW IN UKROM

IO

0 II

12 I1 WAVE LENGTH IN MICRONS

I4

I5

Ib

WAVE NUMllRS IN C U I

Barium phosphate. dibasic, BaHPOi

C.P.

5 b 7 WAVr LBTW N W W

IO

I1

I1 t i WAVE LWSM IN MICRONS

I4

I5

Ib

V O L U M E 2 4 , N O . 8, A U G U S T 1 9 5 2

1273

IW

IO

phosihate, mono67lW Sodium basic, KaH1POd.HsO

ao
C.P

kb3
n

5 a8

~I F

I
I
5
L

v
7

lJ
I

In -v'd
9

1
I 1

20

20

.
I

i0

IW

\
IO

1
I

1
*

I
I

2 5"
z

\J
I

ia
20

*
1

. 1
It

I4

68~

lW

Potassium phobphate, monobasic KHlPOl

C P

IbO

i*)

10

I
2

I b 1 WAVE UNOTH IN *UCRON5

2 3 WAVE UNSTH IN MICROM

0 16 Ib

.\Iagnesium phosphate monohaeic, 3Ig(HzPO&

C . P. c P.

I
0

6 b 7 WAVI W ? H IN MICRONS

ID

I1

I3 W A X M O T H W MICRONS

I2

I4

IS

Ib

Calcium phosphate, monobasic, C a ( H ? P 0 3 ~ . H r O

. \R

1274

ANALYTICAL CHEMISTRY

Sodium rnetaaraenite, YaAsOe

AR

IWW(

I
1

I i

72O0
to
M

Calciuni orthoarhenate, tribasic, Cas(AsOd2

C.P.

l ,
\

4a

f/
I4

XI

0
1

5 b 7 WAVf LfNGTH IN MICRONS

ID

12 I1 WAVE LLNGTH IN MICRONS

IS

Ib

Fodiuni orthoarsenate. dihaiic, Na:HAsO~.iH,O

Unk.

Lead orthoaraenato, dibasic. P ~ H A s O I

C.P.

WAVE NUMPfRS IN CM

X48

1000

*Dp

2100

IWO

S m

110)

,100

Ilm

llm

Imp

9m

W A M NUHIILRS IN C H I UD

7 m

bZS
Im

P o t a w u r n orthoarsenate, inonohasic, KH14a04

iR
M

4 a

m
0
2

5 6 7 WAVE LENGTH IN MICRONS

10

II

I2 I3 WAVE LfN6lH IN HKRONS

I4

I6

Ib

VOLUME

24,

NO. 8, A U G U S T 1 9 5 2

1275

Arsenic trioxide, .-\sr03 Vnk.

Yodirirn

1276

ANALYTICAL CHEMISTRY

Potassium sulfite. K?S0!.2H?0

I,

Calcium sulfite, CaSOi.2H20

C.P.

Barium sulfite, BaSOi

C.P.

Zinc sulfite, ZnSOa.2HnO

C.P

Ammonium sulfate,

(NHWOd

Unk.

1277

Sodiuiii sulfate, Xa?SOd

AR

Potawlurn sulfate, lid304

AR

Calcium sulfate CnS04.2H20

AR

XIangnn-e

aiilfare, JInSOc2HzO
C.P.

1278

ANALYTICAL CHEMISTRY

i
~

Ziroonium sulfate, ZrEOi,4H?O

BO

C.P.

, ,
I
~

,
I 20
0

oi
I

j
I
~

rJ
I
7
I
9

I
IO
I,

I
12

13

15

Ib

fii
!
IO

g i 5
f~
5 J
10

bo;

\
!

I
~

1 1 0

Chroiniu~n potassium ralfare, CI.E(SOI)J.lirR0~.24H:O

__r

,I
*

I
I

bo

Unk.

i
'
_ ,

z l
20-

; . j ~I

i , " 0
1
I

j"
i
V
0
I1

ol

I
1

:
WAM

IC

I
5

I
I5

tEwm

b 7 IN MICRONS

WAVE LENGTH U I UICRONS

,I

I ,

10 I6

Ammonium bisulfate, NH4HSOl

C.P

V O L U M E 2 4 , NO. 8, A U G U S T 1 9 5 2

1279

Sodium biaulfate, XaHSOI

AK

Potassium bierilfate.

KHSOI
AR

Aiiiruoniurii thiosrilfate ( Ni,)..S2OI

C.P

Sodium thiobulfatr, xa:S*03.5H?o

. IR

Potassium thioniilfntr, KnSrOa.Hr0

C.P

1280
I1100
IW

ANALYTICAL CHEMISTRY
k1100

31100

IHD I

WAVE NUMBERS IN CM 2Wa

IHDiHiO

,IS0

l1W

ilW

two

PW I

W A M NUMBERS IN CM BOO

700

b2S

IW

Magnesium thiosulfate, hlgS20a.6H10

C.P.

Barium thiosrilfatr, Be&Oa.H>O

C.P

Sodium ~netahisrilfite, Wa?PtOs

Potassium nietittiisuifite, Ii2SnOr AR

IW,

Arnmoniuni persillfate. (NHI)?S~O~

IO

4 1
!bo7A

.IR

1~
V I

I
~

5 E

10

20

i +

* i
I
4

,
I
5 b

'il
\
1

II

I1

I4

I5

Ib

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2

1281

Potassium persulfata, KnStOs

C.P.

Sodiiini selenite, Pl'alSeOd

Pt i y e

IW

Y *? A
t

selenite, 'I 08ImCopper CuSeOL2HZ0

(0

Y
5 M

Vnk.

40

\ /
I
1

I
~

1
20.

,I
I
I
II I2

\
\/
I3
I4

,
I

20

i I
0

IS

I6

Sodium selenate, SazSe04.10H~O

C.P.

1282
rKa urn
,Cd

ANALYTICAL CHEMISTRY
ma
WAVE NUUlKRS IN C M '
1XD

mo

WAM NUHBERS IN CM'

b% 100

Potassium Belenate, KzSeOi

C.P.

80

60

10

20

5 b 7 W A M LENCTH W MICRONS

IO

I1

I1 I3 WAM LENSTH IN MICRONS

I4

I5

Ib

Copper selenate, CuSeOc5HzO

C.P.

Sodiuiii chlorate, liaCl01

AR

Potassium chlorate, KClOa

AR

Barium chlorate. Ba(C10a)z.HaO

C.P.

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2
WAVE N V H l E R S IN C U ' W A S NUMBERS IN C M I
5

1283

IW

80

L.P.
M

4c

20

5 6 WAVE LENOTH IN MICRONS

7.

IO

II

I2 I3 W A M LLHSTH IN MICRONS

I4

I6

16

5mo
IW
1

UC4

ImO

I=

2mO

lrm

1 4 w

lrn

1100

11m

Iom

10)

IO

p?,
1

f""

$* s
2
$10

',ii

L
10

11 ;ir
x

11

\n,.L'-\, *
&

t
0

I L J
la
I l l

ym

urn

3om
?

250)

2om

1w-

150)

14w
I

13W
l

IlW
, ,

ImO
,

sw

80

> ! .I
z

:/
0 2I+!

8W

7w

)IS

d
~

i IS'*
80

5
n

AR

b0

ZW 2

I #
I

bo

i
'
I
S
b

I
1
I

\,
9

IO

,
I
2
3

?r
I
1

I 0
I2
11

;
l
I

d*

I1

I4

IS

Ib

IW

10'

P
ZW
2

r rL

/?\

-lW

nf

I
/

11 1191
10

I
h

I
,

87 '
10

. i
1

I
I

11
1
b

I\ i

\L
4
S
7
9

r'

,
~

I
I

/*
1 0

1[

I 1
I
I1

Mgd104

I
0 2 * + -

I - '

I
lo

I
0

I
I+

I3

IS

Ib

ANALYTICAL CHEMISTRY

Potassium bromate,

KBrOa

hR

Silver bromate, AgBrOi

C.P.

Sodium iodate, KaIOz

C.P.

10

I9

I1

I ,

IS

Ib

Potasaium iodate. K I O i

Unk.

Calcium iodate, CaIOa.BHz0

O . P .

V O L U M E 2 4 , NO. 8, A U G U S T 1 9 5 2

1285

Potassium periodate, KIO4

C.P.

.4mmonium metnvana.
date, NHcVO:

c. P

Sodiurn rnetavunadate. SnVOz.IHr0

Sodium chromate. KaL'rO4

1286
ym

ANALYTICAL CHEMISTRY
urn
3m0

Ism

WAVf NUMBERS ZmO

M CM'
IUD

,100

1100

I200

1100

ImO

wo

WAVE NUMBERS IN 800

CM'
1m b2S
IW

Im

'rlV$ I

I
I

Potassium chroinate,

KnCrO4
IO

! 5* *z
, ' i9 20

I
~

rA

\\ P,
W

//J

I
0

*
I
3

I
4

W'
,I

10

I
0
I
I4 I5

IO

I1

Ib

l l a g n e j i u n i chroniate,

f iiii

I\

MgCrO~.iH~O
10

C.P.

Barium ciironiate, BaCrOa

C.P.

Zinc rhromate. ZnCr04.7IipO

C.P.

WAM NUMBERS IN C M '

pm

WAVf NUHIERS IN 8W

CMl
1m

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2

1287

136
M

Aluminiini chromate, Alz(CrO4)i

C.P.
S

1 1 I
, I

/I
I
IO

oI
im
Wr(0
10

,'

I
0

1
5 1 7 WAVE W T H IN MICRONS

,I

I,

I5

WAVE LENGTH IN MICRCUS

m>YE

nm

IUD

lua

110

Ilm

IlW

lmo
I

Ho

em

7m

625

1
I 1
~

I 37'
80

Ammoniuni dichroniate, (XHi)zCrSO;

C.P.

!/
S I
10

<

l 'V
1
3

I
I

I
I

~~

\r
I
I1

i : \, d i
I

I \ 1 ,VI
I4

40

m
0

5 b 7 WAVE LINGTH IN MKlOHS

100

'

IO

I1 I3 WAVE LENGTH m WCROHS

IS

IO

iM
1 I
20

!/[ - I !/
1 -

!\!
7T

\
\
I

I38
W

Sodium dichroinate, NatCrtO; .2 1 2 0

C.P

-c

I
,
I

I *
0 .

15 b 7 WAVE W T H IN MICRONS I
9

i i'L
II

rl

/
44

IV
I
I1 I4

m
0

Ib

WAVE LEN6TH IN MKRONS WAVE HUMERI IN W1

iiw

uyx)uDo

mnm

WAVE NUMBERS H

laa

W'
IUD 1100

iim

im

ID^

ua

700

b15
I C 4

im

Potassium dichromate. K~CTSOT

L-nk.

i fbQ

:
Y

;;"
20

40

.
nm
IUD

0
5 WAVE UNOW b 7 IN I ~ O N S

IO

I1

I1 I3 WAVE LEMGTH IN MKROM

WAVE NUMDERS IN C M '

I4

IS

Ib

row urn

WAyt NUMlERS IN C Y '

Imo

IUD

iua

iim

IIW

itw

imo

9m

e m

7m

bl5

Calcirini dichromate. CaCrzO;.SHrO

C.P.

I *Y

II
4

I
1
5 WAVE LINGW

7 WRONS

10

I1

I1 WAVE LENGTH IN MKROHS

1288

ANALYTICAL CHEMISTRY
IW
~ ~

I4I
II S
M

Copuer dichromate, C uCr& .S H 2 0

i P.

1 1 0

m~

5"

$ 1
10

\r
I
I
10

4a

I
IO

I
0

I
I
4

I
I

I
I/

,I

1
0

I5

Ib

>odium molybdate.

SaAfo0~2HzO
.4 R

Iopdurn
Iffl

ludm

lwo

AT
I /

-2
*
~

molybdate, I 43:Im Potassium KzMoo4.mo

M

$@
2

i
\

C.P.

Z"

I
Y
I
4

!~

20

:
F

I
~

\J
9 0

I
I ,

10

'10

l o
,I

S b WAE W T H M UCRONS

1 I1 WAVE LENOlH IN W C U S

IS

-" . I

5 ,pf, J 3 M

I"
10

'
4

, 4 z .4 m nion u ni
I

he1)tamolybdate ~NH~)s~Io;Ou.4HiO

. 1R

10

0
1

5 b 7 WAVE LENOM IN MICRONS

WAVE NUMBfRS IN C M '

IO

I .

I5

I6

WAVE LENOW IN WCRONS

lm

Sodium tungstatr, S~~WOL~IIIO

c P.

(0

10

5 b 7 WAVE LEN6M IN MICRONS

0
,I

WAVE I 1 LEN6TH 1 1 1 11 MKRONI

I .

I5

Ib

1289

Potassium tungstate KzWO4

C.P

Calcium tungstate

Caw04
Pure

WAVE NUMIIERS IN C M '

15% I100

I1W

IM

IIW

..

Iwp

em

WAY WMERS IN CMI 800

7m

'15
I

I
'

-,i

,~

',
'

?
I * ;,

~ , .-

I48
I4
bo

Sodium permanganate. NaMnOc3HzO

C.P

"i,:

1
10

f
0

I
4 5 6 7 WAVE LENGTH IN MICRONS

i
1

IO

I2

I3

I4

WA-

W l H IN Y C I C U S

15

WAVE NUMlElS vi C M '

yxxl

UD)

IW

Mm

1 m

2mo

lxx)

lux)

l l m

,100

IIW

Imo

.m

W A M NWlERS IN W-l

8rn

7m

b25

im

Potassium permanganate, KhlnOi AR

10

I4

= 60

E 5

40

10

10

20

5 b WAVf LEN6TH IN MICRMIS

1,

11 11 W A M LWOTH IN MICRONS

I .

0
I5 Ib

Calcium permanganate, Ca(MnOa)z.4Hn0

C P

1290

ANALYTICAL CHEMISTRY

Bariuui permanganate Ra(3lnOi)z

C.P.

Sodium ferroeyanide, SaiFe(CN)s.lOH.O

C.P

Potas.ium ferrocyanide, KqFe(CX"i).3I1~0 hK

Im

sbx rom '

rn

15m

2rm

10

Ef M
5*

II
I

\,
l

IO

*
I
I

I J

J I

4
I
7
I

I
I

I54
1 1 0
60

Ca!cium ferrocyanide, CarFe(CN)s.l2H>O

i~

Pure

10

,I
I

IIO
O
0
I

I1

,I

I ,

I5

Ib

Potassium ferricyanide, KsFe(CN)s

AR

V O L U M E 24, NO. 8, A U G U S T 1 9 5 2
5WO

1291
IIW
IIW

IMo

1wP

2x4

WAVE NUMBERS IN C M 1 1x4 I r n 1wP

I1W

lca

WAVE NUMBERS IN C M '

VW

aw

7W

615

Sodiuiii coliultiriitritr NarCo iSO.!*

f-

I
1 1

r \ I
1

157Iw
LO

I I

% . K

I
I

'e

I
~

1 -

10

AR

Barium chluride, BaC12.2H10

. iR

1292

ANALYTICAL CHEMISTRY
Table IV. Use of Infrared Spectra in Qualitative Anal>-sis
X-ray

1 . 0
1

Eniiwion

I.; Ca

Sa

Independrnt d n a l y - e . Infrared SaHCOi

Final Cornbined rinalysis

Actual Composition

CaCOr
KSOi
4T14SOI Very poor pattern

WaHCOi

NH4NO.I SO,--Silica eel

.II

Silica gel Sothing Very poor p a t t e r n

Yellon

I'ellon-

Na ICKr20; K N a S C S or N H i K S Cr Ifp(cloi)? Sulfide odor Ph Y Cd SiL?HlOi Bi

AI K*CI.yOi NaSCN AIg(ClO,)? " Pb 1

NazBIO; 10H?O CdS SaBiOx ' !

Ph

KilCrzOi
S-aSCX

RSCS CaS0. L H j O

SatBaO; IOtLO CdS

c ?P

Sa

')

.\IO

Ca I.;
S a '?

Sr 11

K*S?O6 CaCOa PhCrO4 KazSOr Y

Caar PO, I 2

Sh Si
P

ca
C

P?
KaI.03 Ba(K0s A nitrate; prohahly BaPhSOI '? isos)?. possibly SaSOz Other component(s) Possibilities: Another nitrate, SaBrOl. Sa?WO, or K?\VOi. S a l l o O , or K l l o O ~

I .

Ba Na

. 1 1? SI.? 7

To explore this possibility, u series of eight synthetic mixtures wa? prepared and analyzed independently by the three techniques. ( A photographic x-ra!. procedure was used.) This iriformation was then pooled, thr data were re-esamined, and ii combined analysis was obtained. The test was not completel!fair because it, was known that infrared spectra have been ohtained for nearly all the inorganic salts in the laboratory, and that t'hese same salts would he used in making up the mixtures. I n addition, t,he components n-ere mixed in roughly equ:il amounts by bulk. The results are shoa-n in Table IT'. The analysis of misture 3 is discussed in greater detail below. I t is apparent that no one of the techniques by itself is powerful enough to give a complete analysis of even these idealized unknoums. This is partl)- because there was no prior information about the caontent of the samples, and therefore every possibility had to be considered. -1s xith any other anal) much more detailed and reliahlr

Changing the positive ion may produce a different crystallin? arrangement, resulting in a different symmetry or iiitensity of the electrical field around a negative ion. A difference in t,he type or extent of hydration probably alters some of the frequencies. the other hand Hunt, J\-isherd, and Bonham ( 5 ) found that for anhydrous carbonates there is an approximately linear relationship between the wave length of the 11- to 12-micron band and the logarithm of the mass of the positive ion(s). Hunt has kindly pointed out that, the authors' data tit his curve, with the exception of lit,hium carbonate. Characteristic Frequencies of Inorganic Ions. Just as with sulfates and nitrates, most other polyatomic ions exhibit characteristic frequencies. These are summarized in Figure 2 . It is evident that they are distinctive and that they do not have a great spread in wave numbers. Qualitative Analysis. The usefulness of these charactei,istic frequencies in qualitative analysis is obvious. It appeared that the infrared spectrum might give, rapidly and easily, some information about the polyatomic ionE that are present in an unknoivn inorganic mixture. If only one or two compounds are involved, it might, even be possible to narrow the possibilities to a fex- specific salts. It also seemed that a combination of infrared, emission, and x-ray analysis might be very effective. Presumably emission analysis would determine the metals, infrared would say something about the polyatomic ions, and x-ray analysis might, give their combinat,ion into specific salts.
011

Cm-1
600
8 BO;
840:

700

800

900

!OW

1100

1200

1300

1400

2 1
Z Y

c coj

a
3

nco;
SCN'

SILICATES N NOi NO: 4 II

1
1
A

* A L l

17 P Po: 9 HPOq 6 H PO' 5 2. 4 5 SO; 6

NH;

* s

soq
nso;
s20g

IO

3
5

s20j 2 szoi 2 se sao; 2

- k
l i
1 I

L
*LP

s*o; c uo;
ClOi
Br Br 0;

1
3 4 3 3
2
8

I lo;

v voj c, c,o; GE .o= !

Mn MnOZ

,
A
700
800

No h b o i 2 w wo; 3
4

600

900

1000

1100

IPW

1300

1400

Figure 2.
s .

Characteristic Frequencies of Polyatomic Inorganic Ions

m, w. Strong, medium, weak sp. Sharp

* In most, but not all, examples ** Literature value

V O L U M E 2 4 , NO. 8, A U G U S T 1 9 5 2
results can be obtained if there is some advance information ahout the nature of the unknowns. However, Table I\- also shoTvL: that the three techniques are nicely complementary, and th:it together they are capable of providing a considerable amount of information even when such prior knowledge is lacking. Although thrre are two or three surprising errors in the combined :inaI?ws, the over-all rwults are verj- encouraging. It is espec-iall:. noteworth>-that the actual chemical compounds are giveir iri miny ca.vs.
WAVE N U M B S IN CM.1
15W1400 1100

1293
tain possibilities for the x-ray analysis which greatly simplify its interpretation. The advantages of this physical analysis include small sampk requirement, reasonable time, and the ability t o determine the actual compounds in man>- cases. I t is evident, too, t'hat any or all of these three techniques are valuable preliminaries to a ishemica1 analyis on an unknown material, especially a quantitative one. Variability of Spectra. It is not uncommon to find that the spectra of t,wo samples of the same compound are somewhat different. There are several possible reasons for thin.

1100

IIW

1000

In the spectra of sodium IMP~RITIES. cyanide, potassium cyanide, and potassium cyanate (Xos. 21, 22, 23) bands have been marked that are plainly due to 60 the corresponding carbonates and bicar2 bonates. = CRYSTAL ORIESTATIOX. It is well knonm that the spectra of anisotropic y crystals depend on the orientation of 8 the sample. Consequently it is desirable io t o have completely random orientation of the crystallites to avoid such effects. This is an additional rewon for grinding L p d 0 the sample very finely. I5 Ib 8 9 IO 11 12 I3 I4 WAVE LENOTH IN MICRONS PoLnioRPmsai. Different crystalline forms of the same compound are often Figure 3. Portion of Infrared Spectrum of Lead S i t r a t e raDable of eshibitine slightly ., . different infrared spectra ( 2 1 1.. WAVE NUMBERS IN C M ' \ . A R Y I S G DXGREES O F HYDRATIOX. 1200 1100 1000 900 800
~

2 5
y

t>

-4

IO

II
1.1

12

I3

WAVE LENGTH,

Figitre 1 .
I n vier\
caw

Znonialous H a n d in Unknown 3
(:a301 .hould be w r i t t e n C a S 0 ~ . 2 A ? 0

Isi)i\-ii)i..ii, Ti:i.iisrui I.>. S-I,:~?. :in;ilysis of a conipletely I ~ ~ ~ i ~tiiffii.ult o i r i i ~ \vhi~11 ~ thrr(J art' nlow than two unknowi sani~)Ie coniponc~ntr. It is not :i1)plii,:iI)lv t o noncrystallinc material.. ( r f . unknown 2 ) and runs into troul)lc \\-ith substances that gaiii 01' lose water of hydi,ation readily. I n both c5ase.q infmred i i often a rcliable tool. Suhstanc~eslike metal osides, hytirosides, and sulfides gener:illy h:ivcl no sharply defined infrared absorption from 2 t o 10 i d e from possible water and 0-H bands. On the ot1rc.r y are often good samples for x-ray analysis (vf. cadmium sulfide in unknown 4). The principal fault with emission analysis is its great sensitivity : it is frequently difficult t o distinguish between major components :ind impurities. This fact arcounts for t,he surprising oversight 01 cdcium in unknoivn 2 , and tungsten in 8. Infrared examination has advantages over wet chemistry for detecting the more unusual ions, such as BOz-, B407--, SzOs--, and S?Os--, since these are not included in the usual schemes of

Several esamples of variable spectra have been otiserved, lor Lvhirh the muse is not definitely knonn. Tn-o different samples were esaniincd, and proved of potassium metabisulfite, KzS206, to have different, patterns of band intensities in one region (see curve 104). I n potassium carbonate there is a hand a t 880 c m - ' or a t 865 em.-', and in one spectrogram out of a total of ten hoth hands appear. There is no cleai correlation b e t w e n position and water content. Figure3 shows that the mode of preparation is important. It rompares the spectra of two lead nitrate samples, one prepared nornially with Sujol and one with very little Sujol. Differmces near 1300 rm.-l and 880 t o TOO cm-I are striking. This may be an orientation effect. X more baffling case of unexpected variation was ol)serveil with unknon-n S o . 3. In analyzing this by infrared, calcium sulfate dihydrate was missed completely and magnesium percahlorate \\-as reported in its place. The reason is brought out in Figure 4. Pure calcium sulfate dihydrate has a single broad lmnd centered near 1140 cm.-' (8.8 microns), whereas in inisture 3 a strong doublet was observed a t 1080 and 1140 cni.-l Thtx origin of the doublet was puzzling berause no other ($omponcnt of 3 but calcium sulfate has a band near here. Calcium sulfate dihydrate had been run as a Nujol mull and mixture 3 as a dry powder. Reversing each did not change their spectra. Then calcium sulfate dihydrate was mised with each of the other components in turn in the dry state, and the mixtures \wre es:mined as Nujol mulls. It \vas found that the misture with ium thiocyanate gave a doublet. \Tith sodium thiorj-anate there was also a doublet, but it TI-as much less pronounced. It seems unlikely t,hat a chemical reaction between calcium sulfate dihydrate and potassium thiocyanate could account for these peculiar results, bemuse the materials are in the solid state. Two other possible causes are changes in crystal structure, presumably caused by changing the hydrate, and an orientation effect. The following observat,ions seem to rule out variable water content as a cause, and suggest the orientation effect.

The proper sequence in using these techniques is the order cniission, infrared, and then s-ray. The first two present rer-

A calcium sulfate dihydratepotavsium thiocyanat'e mixture heated a t 170' C. for 3 days gave the two bands near 1100 em.-' Only one band was found after the salt plates were separated and t h e mull e ~ p o s e d t o air for an hour.

1294 Another portion of the same heated mixture was esposetl to air under more humid conditions for an hour and then mulled in Nujol: two bands again resulted. This mull was opened to the air for an additional half hour, and only one band was found. \\-hen calcium sulfate dihydrate alone was heated overnight a t 170" C., three bands were found. The sulfate vibration absorbing near 1100 cni.-l is triply degenerate (12), and this may be a case of splitting of the degeneracy as a result of altering the crystal symmet'ry. Finally, potassium sulfate has exhibited a similar variability in this same band,
.
~

A N A L Y T I C A L CHEMISTRY
is evidence that these are 0-H stretching frequencies of the hydroxyl groups attachrd to the rentral atom. B.%RInf CHLORIDE.Several chlorides of the purely ionic type were examined to observe how the hands due to watcr of hydrat,ion varied. Among these was barium chloride dihydrate ( S o . 159). Surprisingly it has a strong band a t 700 cm.-', which )\-as totally unexpected but was c,onfirnied on a second sample. I t is not attributable to carbonate or bicmhonate, hut may tie due to a torsional motion of the w:itcr molecules in tlic lattice. COMPLEX Ioss. The rliaracteristic. frequcncic:; carry over moderately wcll into roinplex ions-for exainple, pot ricyanitie has a band a t 2100 c m - l , and each of the rhree ferrocyanides has one near 2010 cni-'. This is obviously thc stretching frequency of the C S - gi'oupj which in simplr ryanides is 2070 to 2080 c i n - ' Other examples are shon.n in Tnl)le V. CoIiPoazrns WITH So ABSORPTIOS.Sickel hydroxide, fci~ic* oside, cadmium sulfide, and mercuric sulfide have no absorption in the rock salt rcgion aside from watcr mid hydroryl hands.
ACLYO&LEl)(;\I

_-_

Table V. Characteristic Frequencies i n Complex Ions

Complex I o n

cm.- 1
2100 -2010 2140 1923 1336 1430 745
1080

Simple Ion

cm.-1
2070-80

Fe(CN)s--Fe(CKjc---Fe(CS)sNO--

csC?i cs SOP

2070-80
2070-80 1878 820-33 1235-80 1328-80 i26-40
815-35

XO (gac)

847

Ce(S0ds- -

SO?

SO,-

EX1

1260 1420 1530

...

13.40-80

I t is much safer to base arguments on the identity of spectra than on their nonidentity. >lore empirical experience with the spectra of salts from many different' sources should improve t,his situation. Miscellaneous Observations. AXOMALOUS DISPERSION ANU CHRISTIAXSEN FILTER EFFECTS. These have been adequately described in the literature ( 5 , 9). Examples will be seen in the steep-sided band of magnesium carbonate a t 3 microns (No. 13), of sodium thiocyanate near 5 microns (No. 26), and of potassium ferricyanide near 5 microns ( S o . 155). WATERAXD HYDROXYL BAXDS. The sharpness of the \\-ater bands near 3 and 6 microns in sodium and magnesium perchlorate (Nos. 117, l l S ) , and the high value of their 0-H stretching frequency ( >3500 cm.-I), are striking. Apparently t'here is very little hydrogen bonding in these salts. It, is interesting t o note that animoniuni perchlorate (KO. 116), \vhicah forins no hydrate, has a high K-H stretching frequency. Other compounds with sharp water bands are barium chlorate (KO.115) and 1)ai~iuni chloride (No. 159). I n bicarbonate there is a band a t 2500 to 2600 cni.-', in Iiisulfate at 2300 to 2600 cm.-' (very broad), and in HPOI--, H2P04-, HAs04--, and HP;IsO4-at about 2300 em.-' (very broad). Their

The authors are inciel)ted to two colleagues, D. T. P i t i i i x i i and E. S. Hodge, for carrying out t h r x-ray and emission analyses, respectively. Helen Golob prepared many of the curvrs. The Chemistry Departments of the University of Pittsburgh and Carnegie Institute of Technolog!- graciou3ly provided many of t,he samples.
LITERATURE CITED

Colthup, N. E . , ,I. Optical S o c 40 397 (lCJ50'. Glockler, G., Rec. M u d e r n I'hys., 15, 111 (1913). Hersberg. G., "Infrared and Raman Spectra of Polyatomic Molecules." Sew I-ork. D. Van Noatrand Co., 1945. (4) Hihhen, J. H., "The Ranian Effect and Its Chemical -ippIications." S e w York. Reinhold Puhlishinrr Coru.. 1939. ( 5 ) Hunt, J . M., Wisherd. 11.P., and Ronhani, L. k., .is\r., CHicv.,
22, 1478 (1950).

Lecomte. J., AM^. Chim. d c t n . 2, 727 (1948). (7) Lecomte, J.. C'ahiers p h y s . . 17, I (1943!, and referelives cited therein. (8) Sewman, It.. and Idford, R. S.. .I. C'Aem. Phys.. 18, 1 2 i 6 , 1 9 1
(6)

(1950'.

(9) Price, TT. C.. and Tetlow, K. S . , I b i d . , 16, 1157 (194q). (10) Schaefer, C.. and Xlatossi, F.. "Das ultrarote Spektrum," Herlin, Julius Springer., 18:30; repi.inted by Edwards Bi,os., Inc., Ann Arbor, l f i c h . (11) \Vagner, E. L., and I-Ioi,nig, D. F., J . Chem. P h y s . . 18, 296, 305 (1950). (12) Wu, Ta-You, "Vibrational Spectra and Structure of Polyatomic Molecules," 2nd ed., .%nn .%I hor, Mich., J. W. ICcIwat ds. 1946.
RECEITED for review July 3 , 1931
.ici.epted J u n e 7 , 19z2