Professional Documents
Culture Documents
nfrared Spectra
Salt Solutions
of Aluminum
Tech meal
Report 'T#
1\Jo.~~ .
11
:;'J.F.
By.
. Mcintyre ' R.T. FoIey and BF Brown
January 1981
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PERFORMING ORGANIZWTIO
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DISTRISUTION STATEMENT (of the abogrect enterd in Week 20. If different ftsm Roport)
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SACURIT
AIIPSCATIONOF
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THIS PAG@Uibmh
formation),
'4)occasional splitting of the OH bending mode of water.
.5)no direct evidence of anion-cation covalent bonding.
In general, there was no differences at the molecular level between these
aluminum salt solutions that would account for differences in chemical
reactivity
XTI.S
GRA&t
0
1
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Utan- o1nc'ed
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Dib2stribut ion/..
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t~~Availtiity Codes
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UNCLASSIFIED
8SCURITY CLA"IPICATIOW OF T1WIS P&A49MMl04U
* 6"teed)
the solution, per se, is not the determining factor in the activity of
the aluminum salt solution (1).
The objective of this investigation was to attempt to establ'ish
whether or not structural differences at the molecular level could account
for the chemical reactivity. This would involve assessing the effect of
the anion on the structure of the aqueous aluminum salt solution.
The composition of hydrolyzed aluminum solutions :has been studied
extensively.
Smith (3) characterizes the form of aluminum as Ala, Alb, and Alc, the
form predominating dependent on the pH.
++
2 0) 5 0H ,
2 (H2 0) 8 +,
*000
0
qC'4
(.4
-1
0D4 a
0
00
C454
mj
cn
-3-
EXPERIMENTAL
The aqueous aluminum salt solutions in this investigation were prepared with reagent grade materials.
A concentrated
stock so1ution was prepared and less concentrated solutions were made by
successive dilutions.
(6).
Perkin-Elmer double-beam spectrophotometers model number 727 and 397
were used.
parent between 4000 and 750 cm-1 and show a strong absorption at 650 cm
A thin-film was prepared by placing one to five drops of sample (one drop
is equivalent to 2.5 pt) between two IR-TRAN-2 cells and pressing the
cel l s together.
tained just the aluminum salt sample with no reference; the second scan
required an H2 0 reference; and the final scan used a sodium salt reference.
The strong absorption bands of water (see figure 2) were partially compensated for by using a reference solution. The reference solution was prepared by placing one to three drops more than the number of drops used
for the aluminum salt sample.
This
RESULTS
Aluminum Chloride Solutions
The spectra of solutions 0.1107M, 0.27M, and 1.107M in AMl3 were
taken with an H 0 reference and NaCl solution references.
The absorption
Inspection of figure 3,
A--
-IC
-
aa
lb-P
+4
01
IA
I->
0 w
Mo4
-6-
TABLE
A1C1i ABSCRPT:CN
EXSE.ALENT CONCENTRA:ON REFERENCE DESCRITZCN
0.1107 M
5A
pH-3.15
Al-OH-Al stret.
mixed with OH
stret. of H2 0.
w
S
3220
2400
2100
1650
Al-OH-AI stretching
Al-O-Al unsym. stzet.
H20 overtone band
OH bending of E20
WB
2900
ms
2500
w
WB
WB
WB
2050
1450
1200
1000
unsym. stret. of
H20 coord. to Al.
sym. stret. of 520
coord. to Al.
H20 overtone band
SB
S
3500
3125
w
WB
S
M
5B
0.1107 X
0.1107 X
520
H20
5C
0.277 M
H20
p,,2.80
ASSIO:4ENT
35507
3325
3220
2650
2150
1650
820
SB
S
X
H20
FREQUENCY
"
(CM4)
2525
w
S
S
2100
1650
820
Al-O-9 or AI-OH-Al
deformation.
Al-Os-Al stretching
unsym. stret. of
H20 coord. to Al.
sym. stret. of H20
coord. to Al.
320 overtone band
OR bending of 520
-i
0.277 X
M
M
2300
1780
1525
940
2950
2550
1710
w
M
1600
950
3000
'
W
H
M
2550
2400
1980
1720
.600
810
3050
2530
Ws
S
M
2400
1630
810
1.107 M
pH-1.95
NaCI
1.107 H
H20
9A
1.107 M
9B
2900
20M
H20
unsym. stret. of
H20 coord. to Al.
AI-O-H or Al-OH-A1
deformation
unsym. stret. of
120 coord. to Al.
Sym. $treot. of H20
coord. to Al.
AI-O-. or Al-OH-Al
deformation
of
unsym. s&treo.
H20 coord. to Al.
sym. satreat. of H20
cooed.
Al. stret.
Al-O-Al tounsym.
unsym. stret. Cf
.20 coord. to Al.
sym. streSt of H20
coord. to Al.
Al-O-A1 unsym. strat.
OH bending of 920
goI4
0W
N
0 .1
/c
E- N
-8-
3,
tion bands of water found at 3800-3100 cm-1 and 1650 cm-1 in curve A are
absent in curve C when recorded with an H20 reference.
Inspection of
curve A will reveal that several types of OH stretching are found in the
3800-3100 cm- 1 range.
However, a band
in this region is sometimes found when the 2100 cm-1 band is present; this
usually appears near 1840 cm-1 . A band is not always observed in this
region which suggests that it may very well be a result of the water
compensation process.
An absorption band found at 2400 cm-1 appears consistently in all of
the aluminum salt solution spectra; however, this absorption band is not documented
in the literature.
m6 _
-9-
This
When the
These absorp-
tions are found at 3000 and 2550 cm-1 . Again, there is a splitting of the
water absorption band at 1650 cm-1 ; absorptions are found at 1710 and 1600
cm-1 . Figure 6, the spectra of 1.107M AlCl3 , also reveals the major
absorptions of aluminum salt solutions; however, a new band emerges at
2400 cm-1 which is presently attributed to the unsymmetrical stretci. f
Al -O-Al.
Aluminum Nitrate Solutions
The spectra of aluminum nitrate solutions, 0.116M, 0.290M, and 1.159M,
were recorded and the significant absorptions are given in Table II. All
8--
'0i
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34
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2r
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fn
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GI
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u00
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00-
-4
0
0~W
el
~
wl
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--
-32-
oo*
a
a~.
-4
-
o0~~~
-,
-9
(V~
8=
c~,
e*-f
*~
41
,4
--
bi
N
0
t~
1*
I*lo~
04
ci,
-
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41
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*.liii
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-13-
TABLE 'I
A1 (N03)3 ABSORPTION
FREQUENCY
0.30 M
NaNO 3
14
0.290 M
'20
(CM-I)
2900
2500
M
M
W
2000
1480
1000
1.159 M
B20
pHL.70
12
1.159 M
H20
13A
1.159 M
13B
3.0 M
NaNO 3
unsym. stret. of
H20 coord. to Al.
sym. tu:et. of H20
coord. to Al.
H20 overtone band
AI-O-H or Al-OH-Al
defromation
NB
3500
Al-OH-Al stretching
3150
w
w
W
S
unsym. stret. of
R20 coord. to Al.
2400
2075
1860
1650
A -O-Al
unsym. stret.
H2 0 overtone band
1375
N03
w
M
1260
960
pH2.60
11
ASSIGNMENT
SB
3050
2550
w
M
MB
R
M
2400
1890
1550
1330
960
SB
M
3300
2570
w
S
2400
1650
1425
OH bending of H20
Al-O-H or Al-OH-Al
deformation
unsym. stret. of
a20 coord. to Al.
sym. stret. of H 20
coord. to Al.
M
S
1360
940
820
3000
M
W3A
HS
2550
2
2400
1820
MB
M
1510
1320
950
Al-O-Al unsym
st.rut.
NO3
Al-O-H or Al-OH-Al
deformation
Al-OH-Al stretching
sym. stre
of H 2 0
coord. to Al.
Al-O-Al unsym. stret.
OH bending of H 20
No
Al-O-H or Al-OH-Al
deformation
unsym. strut. of
H20 coord. to Al.
sym. stret. of H20
coord. to Al.
A-O-Al unsym. strut.
no-
Al-OH-Al deformation
-14-
Figure 7 is typical.
As a result of using a
NaNO 3 reference, two new bands are found adjacent to the missing N03 band.
These newly observable bands are probably a result of the reference compensation process and not the emergence of new N03 absorption bands; i.e.,
N03 complexed with aluminum or water.
the fact that no additional bands appear near the 1370 cm"1 band in the
spectra using a water reference.
in absorption at about 1500 and 1275 cm-1 , the appearance of new bands
different from the independently absorbing ion at 1370 cm- I (7).
Aluminum Perchlorate Solutions
Aluminum perchlorate solutions, 0.110M, 0.285M, and 1.140M in concentration, were studied with an H20 reference and also with the corresponding
NaClO 4 solution reference.
recorded in Table III.
In
lb
r~d
tn-i5ineCr
oloo
0-0
-16-
Al(CO
TABLE I I
4 13 A3SORPTION
FREQUENCY
0.285 x
2800
H20
(CM-
1.140 H
2600
wWS5
15A
M
W
2350
1820
1120
820
Al-a-Al unsym.
2950
2550
unsym. stret. of
H20 coord. to Al.
sym. stret. of 120
w
w
S
S
2390
2050
1650
1110
820
2920
9
pH-2. 5
0.285 M
ASSI GNENT
coord. to A..
20
520
CIO;
coord. to Al.
Al-O-Al UnsyM. stret.
120 overtone band
O bending of H20
CIO;
unsym. stret. of
920 cooed,
16A
1.140 M
2650
2420
2060
MR
1840
S
V
1120
940
14
820
w
W
pu. l15
H20
16B
strat.
to Al.
stretching
MB
3500
3025
2600
w
W
S
S
w
2400
2050
1650
1120
940
x
M
14
Al-CH-Al
3550
3340
3140
2900
2600
W
W
2400
2000
unsym. stret. of
ord. to Al.
2
sym. strGe-. of H20
coord. to Al.
AI-O-AI unsym. stret.
H20 overtone band
W
S
1820
1650
OH bending of H20
.x
w
111a
920
C.O0
2900
2610
unsym. stret. of
H20 coord. to Al.
w
S
1900
1120
unaym. stret. of
H 20 coord. to Al.
gym. stret. of 520
coord. to Al.
_820
0.111 14
H20
p5-3.10
17
17
0.285 m
18A
H20
pa-2.35
-I
..
stretching
gtzet. of H20
coord. to Al.
sy.
CI0
-17-
TABLE
II
(continued)
FREQUENCY
H20
pH-2.85
18B
1.140 M
pgI.1w
3.0 14
ASSIGNMENT
2910
unsym. stret. of
U20 coord. to Al.
2600
2400
1900
S
S
1650
1100
14
810
NaC1O 4
19
(C.-
coord. to Al.
ON bending of H20
C10
3050
unsym.
2580
sym.
stret. of
H 20 coord. to Al.
strt. of 820
coord. to Ai.
2410
w
w
w
1730
1600
1210
940
2000
Al-a-H or Al-OH-Al
deformation
1.140 K
120
20A
2800
2580
w
Ws
M
Sa
2300
1980
1710
1600
1000
s3
S
3600
3100
14
1.140 M
20B
*11
120
Al-O-Al
unsym. stret.
Al-0-H or Al-O-A1
deformation
unsym.
stret. of
2580
W
w
S
2400
2050
1650
S
w
1100
940
CloAI-O-H or Al-OH-Al
820
deformation
00
a-
00
E-
au
-19-
some cases, as in experiments 16B, 19, and 20B, the frequency is shifted
This may or may not be a function of anion-
is not significantly
is present in most of the spectra between 940 and 1000 cm-1 . A close
inspection of figure 9 will reveal that the ClO
absorption is eliminated
-l
water between 3800-3000 cm
at 3550, 3340, and 3140 cm-1 . The higher frequency band is due to the OH
stretch in water and the two lower frequencies are most likely a result of
AI-OH-Al stretching in polymeric species.
Experiments 19 and 20 revealed a splitting of the OH bending band as
previously observed in aluminum nitrate and chloride solutions.
Aluminum Sulfate Solutions
The absorptions in the spectra from aluminum sulfate solutions 0.036M,
0.125M, and I.lIOM are tabulated in Table IV. These spectra are quite
similar to the absorptions found in aluminum chloride, nitrate, and perchlorate solutions.
The
band located at 2400 cm-1 is present and the difficulty in observing the
deformation band near 940 cm-I is also apparent.
-20-
-4
Cr
04
co
'.44
o0
-E-0
o0r4
-21-
TABLE :V
A12 (SO4) ABSORPTION
EXPERIMENT CONCENTRATION RZFERENCE DESCRIPTION
0.125 M
21A
H20
p5-3.30
21A
H20
21B
0.125 H
32 0
21C
1.110 M
H20
pH52.20
22A
1.110 H
'
20
22B
22C
23
ASSIGIMEN1T
2850
2600
2425
1800
1120
unsym. stret. of
H20 coord. to Al.
sym. stret.
coord.
to Al.of 20
AI-O-Al unsym. stret.
2S04
2950
2625
unsym. stret. of
H20 coord. to Al.
W
S
H
1650
1110
820
OH bending of H20
Soi-
SB
W
M
S
M
3250
2400
1650
1120
820
Al-OH-Al stretching
AI-O-AI unsym. stret.
OH bending of H20
Soz-
.MB
S
3550
3000
2550
Al-OH-Al stretching
unsym. stret. of
520 coord. to A!.
sym. stzet,
of 520
coord.
to Al.
Ws
Ws
S
S
W
2400
1540
1650
1100
980
820
3000
2550
w
S
S
W
2400
1650
1100
980
820
M
W
S
0.125 M
F.EQUE:Jcy
(CM- 1)
1.110 M
B20
MB
1580
appears as a shoulder
on curve A.
0.036 M
H20
2900
M
x
M
WB
2550
1820
1520
.000
unsym. stet. of
H20 coord. to Al.
sym. stret. of H20
coord. to Al.
p5-3.60
AI-0-H or Al-CH-A!
deformation
0.125 M
H20
W1
24
2850
2500
S
S
5
1650
1120
830
-22-
The OH bending
band at 1650 cm- 1 is split and a new band emerges at 1580 cm-1 . This band
at 1580 cm-1 is also found in the spectra of aluminum chloride, nitrate,
and perchlorate and appears distinctly in curve C of figure 9. This scan
was started at 1710 cm-1 and completed at 1200 cm-l, an excess of H20
reference is added prior to this scan.
DISCUSSION OF RESULTS
The absorption spectra of aluminum salt solutions include several
general features:
(1) A broadening of the OH stretching band of water.
(2) A splitting of the OH stretch of water into several absorption
bands.
(3) The emergence of a new absorption band at 2400 cm (4) Occasional splitting of the OH bending mode of water.
(5) No direct evidence of anion-cation interactions.
The ability to eliminate portions of the water absorption spectrum
proved to be quite valuable, particularly in the OH stretching region of
water.
-230
0-
0
0
0
0
0
0
-4
~q.
0~
0
U,
-*
C)
0
0
C)
-4
0
~
0
0-
C~4~
.~
0r~~u~U~
o
4.-
o
0
*
I~.
N
Cd
Ci2
-
0~
1
/
0
0~
I
4-,
0
0~
0 ~
0
-4
~
0
a~
i.-.I
0
0
-4
0
1%
1%)
I
0
I
0
0
-4
I
0
-eij
-24-
1580 cm 1 .
investigation is needed.
Analysis of the absorption spectra for each aluminum salt indicates
that little difference is observed between the individual salts.
Thus, it
may be concluded that anion effects are seemingly absent in the observed
spectra.
completely dissociated.
SO4 , CIOd, and Cl- are covalently coordiWhen these anions are covalently coordi-
nated to a metal a lowering of the anion's symmetry occurs and the appearance of additional absorption bands is observed (7).
of aluminum nitrate and perchlorate reveal that the major absorption bands
of water are eliminated and the unsymmetrical and symmetrical OH stretch
of water coordinated to aluminum can be seen at 2900 and 2500 cm- l.
In
The literature
-25-
species as Al 2 (OH)
stretchings.
+2,
Depending on
the concentration of the four salts, bands at 3100-3200, 3000, 2500, 2400,
1950-1800, and 960 cm-1 were observed.
with the results of Riesgraff and May (4) who observed almost similar bands
and gave the assignments listed in Table V.
1
Fripiat, et al. (5) observed absorptions at 3480, 2965, and 2530 cm-
Their assignments
bound to two aluminum atoms, the 2965 cm- l band is attributed to the stretch
of OH in water coordinated to aluminum, and the lower frequency band, 2530
cm-l , is assigned to the OH stretch of water in the second coordination
sphere.
It is significant that in both studies the band at 3400 cm-1 is considered to signify the existence of the structure Al-O-Al, which would be
H
CONCLUSION
These spectra do provide information on the structure of these aluminum salt solutions which will be of value in the interpretation of results
on their chemical reactivity.
This
-26-
TABLE V *
Spectrum of 40% AlCl 3 -H20 and H20
FREQUENCY (cm-1 )
3400
antisymnmetric stretch of OH
3000
in H2 0 bound to aluminum
symmetric stretch of OH in
2550
H2 0 bound to aluminum
deformation of Al-O-H in AI(H
3+
2 0)
970
1950
600
-27-
ACKNOWLEDGEMENT
The Authors are pleased to acknowledge the support of the Army Research
Office.
REFERENCES
1. K. Sotoudeh, T.H. Nguyen, R.T. Foley and B.F. Brown, CORROSION, in press.
2. C.F. Baes and R.E. Mesmer, "The Hydrolysis of Cations," John Wiley &
Sons, New York (1976).
3. R.W. Smith, "The State of Al(III) in Aqueous Solution and Adsorption
of Hydrolysis Products on a-A12 03 ," Dissertation, Stanford University,
June 1969.
4. D.A. Riesgraf and M.L. May, Applied Spectroscopy, 32(4), 362 (1978).
5. J.J. Fripiat, F. Van Cauwelaert and H. Bosmans, J. Phys. Chem., 69(7),
2458 (1965).
6. F.J. Welcher, The Analytical Uses of Ethylenediaminetetraacetic Acid,
Van Nostand, Princeton, NJ (1958).
7. J.R. Ferraro, "Interpretation of the Infrared Spectra of Inorganic
Molecules," presented at the Infrared Spectroscopy Institute, Canisius
College, Buffalo, NY (August 1961).
8. J. Miceli and J. Stuehr, J. Am. Chem. Soc., 90, 6967 (1968).