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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(6, 7 ) , but unfortunately many of their data are somewhat out
of date and are not always presented in the most useful form.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

ANALYTICAL CHEMISTRY

1254
Table I.

Index to Infrared Curves and Tables of Data

Formula
Boron
hletaborate

No.
1
2
3

Tetraborate

Type
Sulfur (Contd.)
Sulfate

Formula

No.

5
6

Perborate

Misc.

8
9

Carbon
Carbonate

PbCOa
SHiHCOa
NaHCOa
KHCOa

10
11
12
13
14
15
16
17
18
19
20

Cyanide

NaCN
KCY

21
22

Cyanate

KOCX
AgOCN

23
24

Thiocyanate

NHISCN
NaSCN
KSCN
Ba(SCN)z. 2Hz0
Hg(SCS)z
Pb(SCN)z

L1&03

NazCOz
KzCOa
3hfgCOs hlg(OH)n.3HzO
CaCOa
BaCOa

coco3

Bicarbonate

Silicon
Metasilicate
Silicofluoride
Silica gel
Sitrogen
Nitrite

31
32
NazSiFs
SiOr , XHZO

33
34

Nah-02
KNO?
AgNOz
Ba(SOz!z Hz0

36
36
37
38

Nitrate

Subnitrate

39
40
41
42
43
44
45
46
47
48
49
BiOSOz.Hz0

Phosphorus
Phosphate, tribasic

Phosphate, dibasic

Thiosulfate

Metabisulfite

60
61
62
63
64
65

Selenium
Selenite

104

105
106
NazSeOa
CuSeOa, 2H20

107
108

Selenate

(NHhSeOi
NazSeOi. lOHzO
KzSeOh
CuSeOl. 5HzO

109
110
111
112

Chlorate

NaC108
KClOa
Ba(Cl0s)z.Hz0

113
114
115

Perchlorate

NHiClOi
SaClOa, H20
KClOa
Mg(CIO*)z

116
117
118
119

NaBrOa
KBr03
AgBrOa

120
121
122

Bromine
Bromate
Iodine
Iodate

Periodate

123
124
125
KIOi

Vanadium
Metavanadate
Chromium
Chromate

Dichromate

Molybdenum
Molybdate
Heptamolybdate
Tungsten
Tungstate
Manganese
Permanganate

66
67
68

103

Persulfate

50

51
52
53
54
55
56
67
58
59
(NHdzHPOi
hazHPOi.12HzO
KiHPOi
MgHPOi. 3Hz0
CaHPOa. 2H20
BaHPOi

Bisulfate

Complex ions
Ferrocyanide

126
127
128

(NHl)zCrOa
NazCrOi
KzCrOa
MgCrO4.7HzO
BaCrOb
ZnCrOa, 7HzO
PbCrOa
Alr(CrOd8

129
130
131
132
133
134
135
136

(NH4)zCrzOi
NazCrtO~.2H20
KzCrrOr
CaCrzOl.3HzO
CuCrzOr ,2Hz0

137
138
139
140
141

NazMoOi, 2HzO
Kd~foOi.5HnO

142
143

(~Hdahfo7O24.4HzO

144

NanWOi.2HzO
KzWOI
CaWOi

145
146
147

NaMn04.3HzO
KMnOi
Ca(MnOi)*.lHzO
Ba(Mn0h

148
149
150
151
152
153
154
155

71

Ferricyanide

NarFe(CN)a. 10HzO
KdFe(CN)o.3Hn0
c a ~ F e ( C N ) a12Hz0
.
KaFe(CN)s

Orthoarsenate, tribasic
Orthoarsenate, dibasic

Car(.4sOi)z
NazHAsO4.7HzO
PbnHAsOi

72
73
74

Cobaltinitrite

NasCo(N0r)o

156

Hexanitratocerate

(NHdzCe(N0ah

157

Orthoarsenate, monobasic

KHz.4~04

75

Oxide

AszO:

76

NHhCl
BaCln. 2Hz0

158
159

Nujol, fluorolube

160

SbzOa
Sbzos

77
78

(NHI)ZSOSHzO
NazSOa
KzSOa 2Hz0
CaSOa 2Hz0
BaSOa
ZnSOs 2H20

79
80
81
82
83
84

69
70

Antimony
Oxide
Sulfur
Sulfite

Chlorine
Chloride
Mulling agents

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

weak

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

M%Bo~)~.~H~o

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

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

3.

960
1340
1380
3280
4.

~~

5.

w
s
s

w
s
s

Lead metaborate
Pb(B0z)n. HzO
1 0 . 3 s, vb
7.45 m
7.2
Nujol?
3.05 m

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

8.

807
885
1195
1450
3270

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

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

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

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

990
1065
1150
1370
1450
1640
3390

w
s

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

712
775
828
843
.
1000
1075
1130
1260
1275
1360
1420
1460
1650
3330

6.

s
m
vw

1255

Positions and Intensities of Infrared Absorption Bands


s = strong

m = medium

verystrong s h = shoulder b = broad


= KBr region (15-25~) eyamined

vs =

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

Cm. -1

Lithium carbonate
LipCOp
1 1 . 5 8 in
6.92 s
6.7
s

10.

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

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

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.

Calcium carbonate
CaCOa
14.0 w
11.4 s , s p
7 . 0 vs
5.6
vw
3.95 vw

715
877
1430
1785
2530

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

17.

685
840
1410
18.

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

Lead carbonate
PbCOa
14.6 w
1 1 . 9 vw
7.1
YS

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

s
s, sp

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

s
s

w
m
VS,SP

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

E}
5.27 m
5

vw
w (COZ?)
s. b

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

s p = sharp

22. Potassium cyanide


KCN (KHCOa, K ~ C O Simpurities)
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

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

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.

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

30. Lead thiocyanate


Pb(SCN)E
2030
4.93 8. sp
w
2080
4.8

imp. = impurity

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.

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

vs, sp

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

4.9
4.3
4.0
3.4

Cm. -1

vb = verybroad

Potassium metasilicate
KtSiOa
13.0
vw
1 0 . 1 vs, vb
6.15 vw
3.0
m

770
990
1625
3330
33.

Sodium silicofluoride
Na2SiFa
13.73 v s
m,sh
12.7
9.05 vw

728
790
1105

34. Silica gel


SiOz. xHzO
12.5
10.55
9,l5
8.4
6.1
3.0

800
948
1090
1190
1640
3330
35.

s,sh
vw

Sodium nitrite
NaNOz

831
1250
1335

12.03
8.0
7.5

36.

w
w
vs

m, s p
vs

m,sh

Potassium nitrite
KNOz

830
1235
1335
1380
2560
3450

12.05 s , s p
8.1
vs
7 . 5 m, sp
7.25 m
3.9
vw
2.9
vw
37.

833
848
1250
1380

Silver nitrite
AgNOz
12.0 w
11.8 v w
vs
8.0
7.25 vs

38. Barium nitrite


Ba(N0n)z. H20
820
1235
1330
1640
3360
3510

12.2
8.1
7.53
6.1
2.98
2.85

39.

m , SP

;:i5}
6.13 w
5.75 w
w

3410

2.93

40.
836
1358
1790
2428
41.
824
1380
1767
42.

803
835
1348

m
m
m ,sp

Ammonium nitrate
NHiNOa
12.05 w

830
1340
1390
1630
1740

733

w
vs

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

ANALYTICAL CHEMISTRY

1256
Table 11.
vw = very weak

w = weak

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.

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,

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

47.
807
836
1372
1640
3230
3410

726
807
836
1373

Lead nitrate
Pb(N0a)z
13.77 u'
12.39 v w
11.96 w, sp
7.28 w

835
1361
1613
1785
2440
3230

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

50.
816
1325
1380
1640
3390

55.

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

i:: I

56.

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

57.

Lead phosphate, tribasic


Pbs(P0a)z

59.

Chromic phosphate, tribasic


CrPOa. H?O
1030
9.7
vs, vb
1625
6.15 w
3230
3 . 1 E, b

60.

Ammonium phosphate, dibasic


(NHa)zHPOc

Potassium phosphate, tribasic


KaPOi
10.0 vs, vh
1000
6 . 3 w , vb
1590
3180
3.15 vs, b

53. Magnesium phosphate, tribasic


Mga(POajz.4HzO
768
13.05 w, b
887
1 1 . 3 vw, b
1%
1040

1135
1155
1230
1640
3260
3460

%E5]

8.83
8.65
8.13
6.1
3.07
2.9

,"
m

w,sh
w

m
s
m, s h

vb = very broad

sp = sharp

::::}

71.
64.

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

65.

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

697
748
775
833
848
1420
1460
3450

--

72.

Calcium orthoarsenate,
tribasic
Ca,(AsO4)2

Barium phosphate, dibasic


BaHPOa

73.
2440
2700

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

67.

4.1
3.7

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 phosphate, monobasic


NaH2POa. HzO

1640
2850
2820

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

75.

Potassium orthoarsenate,
monobasic
KHzAsOa

750
850
1020
1266
1585
-2275
-2740

--

6.1

m , vb

4 . 2 5 s, b
3.55 s , b

803
840
1040
77.

61.

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

62.

imp. = impurity

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

76.

51.

52.

35

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.

b = broad

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

Bismuth subnitrate
BiONOa. H20
12 27 vw
7.55 s
7.25 vs
6.1
vw
2.95 m, b

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

ah = shoulder

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

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

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

48.

vs = very strong

54.

Barium nitrate
Ba(N0s)t

729
817
1352
1418
1774
2410

s = strong

Cm. - 1

Strontium nitrate
Sr(NOdz

45.

836
1378
1587
1790
2431
3170
3360

Positions and Intensities of Infrared Absorption Bands (Continued)

m = medium

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

68.

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

1105
1410
3075

s. b

Arsenic trioxide
AS?Oa
1 2 . 4 5 vs
11.9
w, sh
9 6
vw, b

78. Antimon pentoxide


Sbr8r
685
1 4 . 6 v w , real?
740
13.5 s , v b
3225
3.1
w, b

69.

iii:

m, b
m, b
vw, b
m, vb
m ,vb
m. vb

Antimony trioxide
Sb2Oa
14.5 w
1 8 . 5 vs
1 0 . 5 vw, b

690
740
950

79.
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

13.3
11.75
9 8
7.9
6.3
4.4
3.85

Ammonium sulfite
(NHa)zSOa. H20
9 . 0 5 vs, b
7 . 0 8 v s , sp
3.25 s

80.

960
1135
1215

Sodium sulfite
Na2S03
10.4
rs,b
11.35 w
8 2
vw

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

1257

Table 11. Positions and Intensities of Infrared Absorption Bands (Continued)


vw

very x e a k

Cni.-'

xv = weak

Nicrons

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

:$; i:::
653

15.3

1100
1210
1625
3400

m = medium

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

87. Sodium sulfate


NazSOa
645
15 5
w
1110
9.0 vs
88. Potassium sulfate*
KzSOa
1110
9 0 vs

667
1010
1130
1630
1670
2200
3410
90,

660
825
1025
1135
3225

Calcium sulfate
CaSOa. 2Hz0

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

Manganese sulfate
MnSOd.2HpO
15.15 m
12.1 s
9.78 nr
8.8

3.1

vs, vb
s, b

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

sh = shoulder

101.

Microns

93.

1080

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

Chromium potassium sulfate


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

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

,
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

89.

very strong

b = broad

= KBr region (15-25p) examined

Cm. -1

627
650
720
770
920
1030

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

m, b
~ sh ,
vw,vb

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

YS =

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

Cm. -1

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

855
945
1020
1100
1160
1630
3170
3390

s = strong

96. Sodium bisulfate


NaHSOh
655
215.3 ni
12.95 vw
773

665
1000
1115
1645
2250
3200
3360
3450

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 )

102.

Barium thiosulfate
BaSzOs.U2O

m
s
m
vw
m

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

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

2:: j>

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

) '"

2080
3390

2.95 vs

100. Potassium thiosulfate


KzSzOs. H20
658
15.2
676
14.8
10 03 s
995
1120
8 95 v s
1625
6 15 v w
3300
3 03 w

Cm. -1

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

11.67
11.42
11.15
9.22
9.0
8.75
7.28
5.73
4.18

89?

Sodium metabisulfite*
Na&Os

4.56

21.91
14..58

.:
I2
a31

18.81 m
1.5. 171

660
fifi7
973

1,j.n /

in.25
0.4.5
8..5
7.9

lofin

11x0

1265

112.

vs

v w , sh

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

104.

1105

9 0.5
R. i

105.
fi?7

702
865

lOR0
1085

-1190
1280
14211
3260

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

4.45
4.23
8.4
7.8
7.0.5

s,sp

3.07

m,

s , 3p

I060

9 1?

1270

7 88

1100

7 7

3300

3 02 w

107.
720
788

112.5
1450
3330

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

109.

@
860
1235
1420
1640
2320
-3140

Ammonium selenate
(NH4)zSeOa
13.0 \

i:;i31

vs,vb

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

938
962

1610
3S40
3570
116.

vs

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

770

114.

vs
w, sp
w,8p

Copper selenate
CuSeOa. 5Hz0

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

113.

935
965
990

vw
vw

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

10.4

YS

t:;:5]

KzS201

14.1

770
858
922
1600
3220
3390

vw
m
vw

115. Barium chlorate


Ba(ClOa)n.H z O

SD

w,sh

v'

106. Potassium persulfate

710

1080
1110
1140
1375
1745
2390

vs
1's

Microns

875
857
103.

imp. = impurity

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

810
824

793
97.

sp = sharp

111.

117.5
1250
8.0
8.1
6.02
3.85
2.88

Rlicrons

vb = very broad

1060
1136
1420
3330

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

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

117. Sodium perchlorate


1100
1630
2030
3570

NaCIOI. HzO
0.1 vs, b
6.14 s , s p
4.93 vw
2.80 s , sp

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

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

ANALYTICAL CHEMISTRY

1258

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


vw

very weak

= weak

m = medium

C m - 1 Microns
I
120. Sodium bromate
NaBrOz
807
1 2 . 4 vs
121.

Potassium bromate
KBrOa
12.65 vs

790

122.
765
797
1280

Silver bromate
AgBrOs
13.08 s
12.55 vs
7 . 2 5 Nujol
?

123.

Sodium iodate
NaIOs

;;; i;:?}

vs

800

12.5

124.
738
755
800

Potassium iodate
KIO?
13.55 vs
13.25 s
12.5 w

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}

126.
848

Potassium periodate
KIOa
1 1 . 8 vs

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.

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

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

s = strong

10.90
6.0
4.7
3.15

= very
= KBr

strong s h = shoulder b = broad


region (15-25p) examined

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

133.

Barium chromate
BaCrOa

i i g ii:z5} vs b
930
3450

142.

135. Lead chromate


PbCrO4
825
855
vw. vb
885
11.3

::::1

vs.b

Potassium chromate
KzCrOh
11.65 w, sh
11.45 vs
10.7 s

very broad

820
855
900
1680
3280
143.

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

825
900
3310
144.

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

sp = sharp

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

;:ii}

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

::%}

145.
810
822
8.50

925
1670
3310

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

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.

794
1640
3390

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

152. Sodium ferroc anide


NaaFe(CN)s. lOd0
1625
6.15 s , s p
2000
5.0
vs
2020
4.95 m, sh

153.
930
995
1630
1650
2015
3410
3510

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;}

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

148.

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.

Potassium permanganate
KMnOd
845
11.85 w
900
11.1 vs
1725
5.8 w
150.

840
905
1625
3470

Calcium permanganate
Ca(Mn03z.4HzO
11.9
m
11.05 vs, b
6.15 8 , s p
2 . 8 8 vs

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

;:%}

154.

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

155. Potassium ferricyanide


KsFe(CN)e
2100
4.77 s

847
1333
1430
1575
1645
2665
2780
3450

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

157.

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.

138.

imp. = impurity

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

156.

vs, b
m,sh
s,sp
m, b

750
940
1625
3450

10.75 s , s h
2.9
w

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

vb

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.

Sodium chromate
NaKrOd
14.7 m

i?::
11.2

vs

1410
1780
2000
2860
3070
3150

Ammonium chloride*
NHiCl
7.1
8 , sp
5.75 w,b
5.0
vw
3.5
m

::?!}

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

2918
2861
1458
1378
720

160. Nujol
3.427 s
3.495 a
6.859 m
7.257 m
13.89 w

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)

ANALYTICAL CHEMISTRY

1260
IW

/4n
I

10

A~

Z;\ $U:

40

f~

20

~I

500)

low

Urn

2SW

5
6
I
WAVE LENGlH IN MICRONS

WAVE NUMBER5 IN CM'


,5WI,W
?OW

I200

IIW

Sodium metaborste,
NaBOz

;I

C.P.

= bo

10

liW

Iwo

I1

12

I1

1s

I4

' 0

WAVE NUMBERS IN CMI


9w

aw

b2S

700

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

5
b
7
WAVE LENGTH IN MICRONS
WAVE NUMBERS IN CM

5wo

100)

Urn

2100

lwa

Ism

,104

I1W

I100

IO

IIW

Iwo

12
I1
WAVE LENGTH IN MICRONS

11

9w

I4

WAVE NUMBERS IN CM'


I00

IS

7w

I6

b2S
100

lM

Lead metaborate,
Pb(BOdn.Hz0

IO

IO

560

bO

C.P

g*

40

20

20

5
6
7
WAVE LENGTH IH 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 NUMIRS IN C H
500)

(ooo

100)

2Mo

low

,5Wl,W

1100

IIW

llW

Iwa

9W

WAVE NUMBERS IN CM1

ud

IM

7w

625

Potassium tetraborate
KgBdO?.5HzO

IO

iz *
z

1"

20

0
WAVE LENGTH IH MICRONS

WAVE LENGlH

IH

MlCRMlS

P.

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

1261

IW

80

i
ZbQ

I!

"

10

C.P.
M)

20

0'

IW.

\l/*la/ !1

11

IO

10

II

11

I1

I4

I.

I5

IO

V "

I
V

ilo

'1'"Sodium perborate,

60/

?;aBOa.lHdI
Y

E'O

'

'I

10

s5

Manganese tptraborate,
MuB4&.8HzO

6'*

II

L'

f, '0.

I
I

\AIL

1
I

(0

:L/;

C.P.

lh/--,

10

I
I
I

I1

I
I1

I1

10

0
I5

I4

Ib

Boric acid, HiBO


02.

SVX
100.

IO

1VX

4oW

<

ZSW

1VX

r
F

z
p7f

'

IIW l u x )

Q'

100.'

-#-10.

fa-

zi

615
loo

7m

10)

'm

10

I
I
7

I5W

lux)

1lW

1100

1100

10

11

IVX

I1

I4

700

iw

(w

I5

Ib

615

1'0

AR

u
64

40

lo

0
9

Lithium carbonate,
LizCOa

IO

Pure

I \,

i *-

Boron nitride, B N

1
~

9w

I
10

loo0

liW

uI

'Ob

IlW

c
L

1100

I1

I1

IS

Ib

ANALYTICAL CHEMISTRY

1262
WAYL NUM?ERS IN C M '

5ccO

wO

3w0

15W

iico

1 5 w 1 4 c a 1100

lw(.

WAVE hLM5ERS Ih C U I

iom

)loo

FCO

100

6CC

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

2m

ISWilW

1004

I700

IIW

ll00

IW

IOW

9w

IW

IM

7
80

b15

15Im Barium carbonate.

BaCO:

-80

AR

"

5.f

I
~

1"
Y

10

--~
-

1-1

!
10

41

b
1

WAVE LENGTH IN MICRONS

I 1

I1
WAVE LENGTH IN W C R M I S

10

I5

b0

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

I,263
WAVE NUMlfRS IN u ( l

WAVE NUMBERS IN C M '

5
io0

Cobaltous carbonate,
COCOl

Unk.

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.

ANALYTICAL CHEMISTRY

1264
IW

Sodium cyanide,

NaCN
80

'Na,CO.

k.

NaaCO3
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

mPY- I,/

fM

'

Ammonium thiocyanate,
2 5 1 m

"

AR
'D

E"

10

10

10

I
0
1

'

8
WAVE LENGTH IN' MICRONS

10

II
I1
WAVE LENGTH IN MICRONS

14

0
5

NHaSCN

80

-7

Ib

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

1265

Sodium thiocyanate,
SaECS

Potassium thiocyanate
KBCS
AR

WAVE NUMBERS IN C M '


XCC
IW

Urn

3wO

1SW

3000

ISW

I4W

12w

IIW

I W

Iwo

9w

WAVE NUMIIERS IN CM
8W

b25

IW

100

IO

(0

(0

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

f
e

5"
$
10

20

sox 4ccc

3mo

25w

5
h
7
WAVE UN6TH IN MICRONS
WAVE NUMBERS IN CM
2000

I5W

l4W

l3W

17W

IO

IWO

I!

Vw

I2
I3
WAVf LENGTH IN MICRONS

I4

WAVE NUMOERS IN CM1


8W

lb

bl5
lW

703

lW

1-

Mercuric thiocyanate,
Hg(SCS)*

(0

Pure
(0

I"
Y

20

10

SWO

IWO

4wO

ISW

5
6
7
WAVE ttNGrn IN M~CRONS

WAVE NUUBERS IN C M '


lD00
1503

I+W

IIW

I1W

lax,

9w

It
I3
W A S Wlli IN MICRONS

15

I4

WAVE NUMBERS IN C M '


SOD

7w

Ih

hl5

-01

lop

Lead thiocyanate
Pb(SCN)*

IO

C.P.

kt4
n

<

rm

4Q

20

0
1

5
L
7
WAVE LENGTH IN MICRONS

IO

I1

I1
11
WAVE LEN6TH IN MICRONS

Ib

IS

Ib

ANALYTICAL CHEMISTRY

1266

Sodium metssilicate,
NarSiOr5HaO
O.P.

Potassium nietrtsilicate,
KrSiOi
O.P.

Xm
IW

Io.

1800

u*yI

1100

100

Irn

110)

Ilm

la4

no

rr-"---/
*

8s "

Iyo

lOm

1W

800

(11

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

33

SazSiFe
w

a.p.

?-

I'

1
L

44

20

20
~

WAVE NUMBERS IN

I1

CM

ll

I+

I&

Ib

WAVE NUMBERS IN CMI

Silica gel,
SiOmHrO

WAVE LM6W IN MICRONS

WAVE U N 6 W IN MICRONS

5
IW

Sodirim nitrite, NaNOi


H

44

10

5
WAVE

LWOM IN HICRM

II

WAbl IuN6W IN I MCRONS


3

It

C.P.

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

1I

w
C.P.

fi

I
20

37IW Mver nitrite, AgKOz

la
20

5
6
7
WAVE LEWTH IN UlCRONS

IO

1
2
WAVE LENGTH IN WCRONS

14

I5

WAVE NUMBERS IN CM I

WAVI NUMBERS IN C U I

Ib

Barium nitrite,
Ba(N0:hHsO
80

C.P.
Y

20

5
6
WAVE LLNGTP IH H U M S

0
IO

II

I2

WAVE ENOW IN

I1

mcRoNs

I4

I5

Ib

im

Animonium nitrate,
NHaKOs
W

C.P

20

5
WAVE UNOIH

7
MICROHS

WAVE NUMBERS IN C U

IO

II

12
I>
WAVE LENOM IH MICRONS

I4

Ib

WAVE HUMBEIS IH C W

Sodium nitrate, KaNOa

AR

a
WAVf YHCM IN MICRONS

ANALYTICAL CHEMISTRY

1268
5wO
W

UDO

105)

2SW

2mO

ll00

IXd

rn

im

b25

700,

loo

l P \ w d '4l Io

//

1'

60

IlW

llm

1100 l4M

A 11

bo/

;
g
S

Potassium nitrate,
KSOa

'

401

10

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

(D

10

10

5
b
7
WAVE LENbTH H MICRON5

10

It

I1
I1
WAVE LEN6lV IH MICRMIS

16

IC

1b

Barium nitrate, B~.:(?jod?


A It

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

80

z
2

bo-

i9
20

no

i'

3-

\r'

AR

Ferric nitrate,

Fe(S03)3.9H20
*7
49
"
- '

\ /

,
4a

"

'

W A d LENGTH IH' MICRONS

20

I
V

2
I3
WAVE LENGTH IN MURCUS

0
Ik

I5

Ib

Bismuth subnitrate.
BiOSO3.HnO

Unk.

ANALYTICAL CHEMISTRY

1270
IW

80

EM

'0

\J

"

f
Y

5 M Mo(
I w - ' I (

" '

3oW

, 2'W'

'

3- ji !
L:j

lol
0

swo k4f8
IW

80

'

!'

10

0
2

I4

IS

Ib

i 52lw

2100

zoo0

lua

Ism

I2W

IlW

IlW

IO

Imo

11

c. P

40

I20

i
I1

I2

/--..,

b25

700

153r

I
J

i?

ba

I
I

C.P.

4a

Magnesium phosphate,
tribasic,
Mga(POdyAHz0

I8O

~1

t
5
b
WAVE LEN6TH IN MlCRMiS

' 0

15

I*

aw

(00

-$

Potassium phosphate.
tribasic, &PO4

10

IC/
I

I; I

I
I

:i
I I
I

I2
I1
WAVE LENGTH IN WCROHS

Z"

\\

'A

P
g,
g

I1

b-,*

?I

:1*
1m

" .

4a

/I

a-

I'\

\ I

\ I
I

80

b4

20

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

AR

/
( 1

10

0~
2

Eodium phosphate,
tribasic, NalP04.12H;O

51:

I
IO

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

WAVE NUMltRS IN C M '

tmo

2100

Ima

IW

I-

IZW

IIW

IN

tW

imp

iim

IW

/
ir\ 7
1
.
m
.,
,

qoo
LIS

Nickel (ow) phosphate,


tribasic,
Nia(POdz.7 H?O

/ *

I
I

/,

\ \,

L,

7
I

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

5wO

ION

IWP

25W

WAYZ NUMBfRS
ZOW

H CM
15w

Iuc

Lm,

1100

lIW

Iwo

WAVE NUMBERS IN C M '


9w

100

IN

b15

phosphate, tribasio,
58Iw Lead
PbdPOdz
IO

C.P.

I?

I
I

'

i*
10

I
5
b
7
WAVE LENGTH IN MICRONS

12
I1
WAVf LENGTH IN HhROlll

0
I4

I5

Ib

WAVE NUMBERS IN CM

5
iw

(0

Chromic phosphate,
tribasic,

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

A N A L Y T I C A L CHEMISTRY

1272
WAW W

S IN CU-

l5a

IUD

I1rn

I200

llrn

WAVE NUMDERS IN C U I

700

100

Im,

b25

100

100

80

Sodium phosphate, dibasic, NaSHPO 1.12 H20


C.P.
U

I"

10

I
1

5
b
1
WAVr W T H IN UCRONS

IW

10

I1

I2
I1
WAVr LW6W IN MICRONS

I4

I5

Ib

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

1m

2x0

WAYS NUMBERS IN CU I

WAVE NUMBERS IN C U I

2wo

5
ID3

10

Calcium phosphate,
dibasic. CaHP04.2H20

m
C.P

jM
f

Lo

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

phosihate, mono67lW Sodium


basic, KaH1POd.HsO

IO

ao

kb3
n

lJ

~-

5 a8

20

.
I

In
-v'd

20

I
L

lW

68~

.-

\J

2
5"

i0

IO

20

I
5

ia

IW

C.P

Potassium phobphate,
monobasic KHlPOl
C P

IbO

i*)

10

I
b
1
WAVE UNOTH IN *UCRON5

It

2
3
WAVE UNSTH IN MICROM

I4

16

Ib

.\Iagnesium phosphate
monohaeic, 3Ig(HzPO&
cC . P.
P.

I
0

6
b
7
WAVI W ? H IN MICRONS

ID

I1

I2

I3
W A X M O T H W MICRONS

I4

IS

Ib

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


.\ R

ANALYTICAL CHEMISTRY

1274

Sodium rnetaaraenite,
YaAsOe

AR

IWW(

I
1

72O0

Ii

Calciuni orthoarhenate,
tribasic, Cas(AsOd2

to
C.P.
M

4a

l,
\

f/

XI

0
3

5
b
7
WAVf LfNGTH IN MICRONS

ID

12
I1
WAVE LLNGTH IN MICRONS

IS

I4

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

Sm

110)

Ilm

,100

llm

Imp

9m

W A M NUHIILRS IN C H I
UD

7m

bZS
Im

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

iR
M

4a

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

aiilfare,
JInSOc2HzO

XIangnn-e

C.P.

ANALYTICAL CHEMISTRY

1278

Ziroonium sulfate,
ZrEOi,4H?O

BO

C.P.

,
,

oi

rJ

I 20

IO

I,

12

13

15

Ib

fii
!

IO

g i
5

bo;

10

z l
20-

ol

,I

'

bo

; . j ~I

__r

f~
5
J

110

I
5

WAM

tEwm

b
7
IN MICRONS

j"

i
0

Unk.

i
,
"
0

_ ,

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

I1

,I

WAVE LENGTH UI UICRONS

IC

I,

I5

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

ANALYTICAL CHEMISTRY

1280
I1100

IHD

31100

k1100

IW

WAVE NUMBERS IN CM
2Wa

IHDiHiO

,IS0

l1W

two

ilW

PW

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

.IR

1~

!bo7A

5
E

10

20

+i

* i

I
~

I
4

'il

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

5 M

40

Vnk.

1
20.

,I

I
20

\/

i
I

(0

\ /

selenite,
'I 08ImCopper
CuSeOL2HZ0

Y *? A

II

I2

I3

I4

IS

I6

Sodium selenate,
SazSe04.10H~O
C.P.

1282

ANALYTICAL CHEMISTRY
rKa urn

ma

WAM NUHBERS IN CM'

WAVE NUUlKRS IN C M '


1XD

mo

b%
100

,Cd

80

Potassium Belenate,
KzSeOi

C.P.
60

20

10

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

1283

WAVE N V H l E R S IN C U '

W A S NUMBERS IN C M I

IW

80

L.P.
M

4c

20

5mo
IW

ImO

UC4

I=

$10

11m

1100

Iom

I2
I3
W A M LLHSTH IN MICRONS

10)

sw

8W

I4

16

I6

&

11

11 ;ir

lrn

14w

II

IO

\n,.L'-\,
*

f""
1

',ii

s$ *

7.

lrm

2mO

p?,

IO

5
6
WAVE LENOTH IN MICRONS

I
LJ

10

t
0

ym

1w-

urn

3om

250)

2om

150)

14w
I

13W

la
I

IlW

ImO

> ! .I

80

:/

, ,

7w

)IS

i IS'*

80

AR

b0

I #

2Z W

'

I
0

\,

IW

r rL

0
I2

I1

87 '

ZW
2

10

nf

I\ i

11
1

\L

I
I

IS

r'

1[

I
1

Mgd104

11 1191
10

I1

Ib

-lW

I
,

/*

I - '
I

10

02*+-

I
0

I4

/?\

d*

02I+!

11

10'

I
-

1
I

;
l

?r

IO

bo

I3

lo
I+

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

ANALYTICAL CHEMISTRY

1286
ym

urn

3m0

Ism

WAVf NUMBERS
ZmO

M CM'
IUD

,100

1100

Im

I200

1100

wo

ImO

WAVE NUMBERS IN
800

'rlV$
-I

!5 ** z

1m

b2S
IW

IO

Potassium chroinate,

KnCrO4
I

rA

\\ P,

i 9,'

I
20

CM'

I
4

IO

//J
O

10

W'
,I

I1

I
0
I

I4

I5

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

Aluminiini chromate,
Alz(CrO4)i
M

C.P.

1
1
I

-/I
,
I

oI

,'

m>YE

Wr(0

im

5
1
7
WAVE W T H IN MICRONS

nm

IUD

I,

lua

Ilm

110

IlW

10

!/

lmo

em

Ho

625

7m

I 37'

l
'V

~~

10

I1

I1
I3
WAVE LENGTH m WCROHS

40

Sodium dichroinate,
NatCrtO; .2 1 2 0

I38
W

C.P

-c

IS

I4

1-

rl

i i'L

44

IV

0
5
b
7
WAVE W T H IN MICRONS

mnm

uyx)uDo

IO

20

I *

7T

1 -

1I

!\!

!/[
- I
!/

\1 I
,VI

5
b
7
WAVE LINGTH IN MKlOHS

IO

iM

\r
I

C.P.
S

'

100

i : \,
d i

Ammoniuni dichroniate,
(XHi)zCrSO;

80

1
~

I5

WAVE LENGTH IN MICRCUS

<

,I

IO

WAVE NUMBERS H

laa

II

I1

I4

Ib

WAVE LEN6TH IN MKRONS

W'
IUD

1100

im

iim

WAVE HUMERI IN W1
iiw

ID^

ua

b15

700

im

IC4

Potassium dichromate.
K~CTSOT
L-nk.

i
fbQ

;;"

40

:
Y

20

row urn

nm

0
5
WAVE UNOW

b
7
IN I ~ O N S

WAyt NUMlERS IN C Y '

IUD

Imo

IUD

iua

iim

IIW

itw

IO

imo

I1

I1
I3
WAVE LEMGTH IN MKROM
WAVE NUMDERS IN C M '

9m

em

IS

I4

7m

Ib

bl5

Calcirini dichromate.
CaCrzO;.SHrO
C.P.

I *Y

II
4

I
1
5
WAVE LINGW

WRONS

10

I1

I1
WAVE LENGTH IN MKROHS

ANALYTICAL CHEMISTRY

1288

IW
~

I4I

Copuer dichromate,
C uCr& .S H 2 0

II S

110

i P.

\r

m~

5"

$ 1
I

4a

10

I
I

IO

10

I/

,I

1
0

I5

Ib

>odium molybdate.

SaAfo0~2HzO
.4 R

Iopdurn

-2

lwo

ludm

Iffl

AT

$@

Z"

!~

20

C.P.

molybdate,
I 43:Im Potassium
KzMoo4.mo

\J

10

'10

'

-" . I

S
b
WAE W T H M UCRONS

l o

,I

1
I1
WAVE LENOlH IN W C U S

I,

IS

,4z .4 m nion u ni
I

53 -,pf,
J
M

I"

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

.1R
4

10

10

5
b
7
WAVE LENOM IN MICRONS

IO

I.

I5

I6

WAVE LENOW IN WCRONS

WAVE NUMBfRS IN C M '

lm

Sodium tungstatr,
S~~WOL~IIIO

(0

c P.
M

10

5
b
7
WAVE LEN6M IN MICRONS

0
,I

WAVE I 1LEN6TH 111 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

em

Iwp

..

WAY WMERS IN CMI


800

'15

7m

I
'

-,i

,~

',

I48

~,-.--

I4

Sodium permanganate.
NaMnOc3HzO
C.P

bo

'

"i,:

I
*
f

10

;,

5
6
7
WAVE LENGTH IN MICRONS

IO

WA-

WAVE NUMlElS vi C M '


yxxl

Mm

UD)

IW

1m

2mo

lxx)

lux)

llm

,100

IIW

Imo

.m

I3

I2

I4

15

W l H IN Y C I C U S

W A M NWlERS IN W-l

7m

8rn

b25

im

10

I4

E
5

AR

= 60

Potassium permanganate,
KhlnOi

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

ANALYTICAL CHEMISTRY

1290

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

sbx rom
'

rn

2rm

15m

Im

10

Ef M

II

\,

110

Pure

i~

60

10

,I

IO

IIO

I
I

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

I54

J I

I
J

5*

I
5

O
9

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

IMo

1wP

2x4

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

I1W

1291
IIW

IIW

WAVE NUMBERS IN C M '

lca

aw

VW

615

7W

Sodiuiii coliultiriitritr
NarCo iSO.!*

f-

I
1

LO

1 -

%
. K

I
I

157Iw

r-\
I

'e

I
~

10

AR

Barium chluride,
BaC12.2H10

.i R

ANALYTICAL CHEMISTRY

1292

Table IV.
1.0
1

Eniiwion
Sa

I.;
Ca

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

Use of Infrared Spectra in Qualitative Anal>-sis

Independrnt d n a l y - e .
Infrared
SaHCOi

Final
Cornbined
rinalysis

X-ray

Actual
Composition
WaHCOi

CaCOr
KSOi

NH4NO.I
SO,--Silica eel

4T14SOI
Very poor pattern

Silica gel

.II

Ph

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

Sa

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

Sothing
Very poor p a t t e r n

KilCrzOi
S-aSCX

RSCS
CaS0. L H j O

NazBIO; 10H?O
CdS
SaBiOx '!

SatBaO; IOtLO
CdS

')

c ?P

.\IO

Ca
I.;
S a '?

Sr 11

K*S?O6
CaCOa
PhCrO4
KazSOr Y
Caar PO, I 2

Sh
Si
P

ca
C

P?

Ba
Na

I.

.11 ?
SI.? 7

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 ~

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.

Cm-1
700

600
8 BO;
840:

c coj

nco;

SILICATES
N NOi
NO:

900

1100

!OW

1200

soq

*A
L l

II

nso;

3
5

ClOi
Br Br 0;

I lo;

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

* s

- k
l
i

-1-

1
3
4

3
3
2
8

600

Figure 2.

700

800

900

1000

1100

IPW

1300

1400

Characteristic Frequencies of Polyatomic Inorganic Ions

m, w. Strong, medium, weak


sp. Sharp
s.

L
*LP

No h b o i 2
w wo;
3

Mn MnOZ

s20j 2
szoi 2
se sao;
2

s*o;
c uo;

IO

s20g

NH;

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

1400

1300

-21

SCN'

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

800

* 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

1293

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

1100

IIW

1000

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.

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.
CRYSTALORIESTATIOX. 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
~

t>

-4

IO

II

WAVE LENGTH,

Figitre 1 .
I n vier\

caw

12

2
5
y

I3

1.1

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
o i r i i ~ \vhi~11
~
thrr(J art' nlow than two
unknowi sani~)IeI ~ ~ ~ i ~tiiffii.ult
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

The proper sequence in using these techniques is the order


cniission, infrared, and then s-ray. The first two present rer-

Several esamples of variable spectra have been otiserved, lor


Lvhirh the muse is not definitely knonn. Tn-o different samples
of potassium metabisulfite, KzS206,were esaniincd, and proved
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.

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 dt o air for an hour.

A N A L Y T I C A L CHEMISTRY

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,
.

_-_

Table V. Characteristic Frequencies i n Complex Ions


Complex I o n

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

cm.- 1
2100
-2010
2140
1923

847

Ce(S0ds- -

1336
1430
745

SO?

1080

1260
1420
1530

Simple Ion

csC?i cs -

XO (gac)

SOP
SO,-

cm.-1
2070-80

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

...

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

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.
COMPLEXIoss. 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

EX1

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.,C H i c v . ,
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