Mikrochimica Acta [Wien] 1983 I, 55--64

9 by Springer-Verlag 1983

Department of Chemistry, Faculty of Science, Okayama University,

Tsushima-naka, Okayama-shi, 700 Japan

Spectrophotometric Determination of Aluminium with

Bromopyrogallol Red and a Quaternary Ammonium Salt:
Determination of Aluminium in River Water
By
Czeslaw Wyganowski*,ShojiMotomizu,and Kyoji T6ei
With 5 Figures
(Received May 30, 1981)

We have already proposed spectrophotometric determination of

aluminium with Pyrogallol Red and Bromopyrogallol Red in the
presence of cetyltrimethylammonium bromide 1,2, cetyldimethyl-
benzylammonium chloride or Triton X-1002. Cetyltrimethylammo-
nium bromide gave the largest sensitizing effect. These methods are
sensitive and reproducible, but the p H range for the complex
formation is very narrow.
Aluminium and iron have been determined in river and sea-
water spectrophotometrically with Pyrocatechol Violet 3,4, and with
Pyrogallol Red and zephiramine (tetradecyldimethylbenzylammo-
n i u m chloride)5; in these methods the co-extracted reagent was
removed from the organic phase by addition of suitable amounts
of chloride, resulting in a considerable improvement in sensitivity
and selectivity. Although these extraction methods are very sensi-
tive they are also rather lengthy and inconvenient.
In this paper, we report a very simple and rapid method for
aluminium, based on reaction with Bromopyrogallol Red and n-
tetradecy|trimethylammonium bromide to form a ternary complex.
T h e method can be applied to trace determination of aluminium in
natural waters.

* Institute of General Chemistry, Technical University, 90-924 Lddz,

Poland.

0026-3672/83/8301/0055/$ 02.00
56 C. Wyganowsky et al.:

Experimental
Reagents
BromopyrogaIlol Red (BPR) solution (3.5• Dissolve 20 mg
of the reagent in 50ml of ethanol and dilute with water to 100ml.
Prepare freshly each day.
Standard aluminium solution (3.71 x lO ~ M). Prepare a stock solution
by dissolving 4.40g of aluminium potassium sulphate 12-hydrate
[A1K(SO4)~" 12H20] in 50 ml of distilled water plus 0.5 ml of concentrated
sulphuric acid, and dilute with water to 250 ml. Prepare the working
solution by accurate dilution.
Aqueous quaternary ammonium salt solutions. Cetylpyridinium bromide
(CP), 2.6 • 10 -a M; trimethylstearylammonium bromide (TSA), 2.8 x 10-3M;
n-tetradecyltrimethylammonium bromide (TDTA), 3.0 • 10 -3 M; n-oetyl-
trimethylammonium bromide (OTA), 3.9 • 10 .3 M; dodecyltrimethylammo-
nium chloride (DTA), 3.8 • 10 -3 M; n-decyltrimethylammonium chloride
(n-DTA), 4.2 • 10 -3 M; 2,3,5-triphenyltetrazolium chloride (TPT), 2.2 •
10 -3 M; tetradecyldimethylbenzylammonium chloride (zephiramine) 2.7?<
10 -3 M were used. The salts were dried at reduced pressure (about 5 mm
Hg) and about 50 o C to constant weight, and then dissolved to give 0.1%
solutions.
Mashing agent. Aqueous solutions of hydroxylammonium chloride
(0.05 M) and 1,10-phenanthroline (0.01 M) were used.
Buffer solutions. An aqueous 10% hexamine solution, adjusted to
pH 5.5 or 4.7 with dilute hydrochloric acid was used. In examining the
effect of pH, the solution was adjusted to the desired pH with hydro-
chloric acid or ammonia solutions.
All reagents used were of analytical reagent grade.

General Procedure
Dilute a sample of test solution, containing 2.5--10/~g of alu-
minium, to about 10ml in a beaker. Add by pipette 3 ml of
3.5 x 10 4 M BPR, 6 ml of 3.0 x 10 -3 M T D T A and 2 ml of buffer
solution. Adjust the p H to 5.5 with dilute ammonia, transfer to a
25-ml standard flask, dilute with water to the mark and mix. After
10 min, measure the absorbance at 623 n m in a 10-ram cell against
a reagent blank.

Results and Discussion

Absorption spectra. Aluminium forms a 1 : 1 complex with

Bromopyrogallol Red in acidic medium 2. T h e presence of quater-
nary a m m o n i u m salts shifts the absorption m a x i m u m from 525 to
608 n m for O T A and T P T , from 525 to 613 n m for n-DTA, and
 Spectrophotometric Determination of Aluminium 57

from 525 to 623 n m for T D T A , TSA, DTA, CP and zephiramine.

T h e absorption spectra of the A1-BPR-TDTA complex and the rea-
gent blank are shown in Fig. 1. Only the B P R - T D T A system gives
a low reagent blank absorbance.

0~c

0.8

2
0.7

0.6

~ 0.5
r~

.8 O.4

0.2

0.2

0.1

I I I
0 5 0 550 600 550 700
Wavelength, nm

Fig. 1. Absorption spectra (pH 5.5) of (1) Bromopyrogallol Red-n-tetradecyltri-

methylammonium bromide system, measured against water, C B P R = 4 . 2 x 10 -a M ,
CTDTA=7.2xl0-4M; (2) ternary complex, CAI=l.48x10-SM, CgpR=4.2x
10 -5 M , CTDTA=7.2 X 10 -4 M , m e a s u r e d against a blank

Effect of pH and time. T h e absorbance and wavelength maxi-

m u m of the ternary complex change with pH, but are constant in
the p H range 5--6.2 (Fig. 2). H e x a m i n e was chosen as the buffer
and does not affect the absorbance of the ternary complex.
Even with a threefold excess of BPR, the reaction takes about
10 min to reach completion. A very large excess of n-tetradecyl-
trimethylammonium bromide (at least a 5 0 : 1 mole ratio to alu-
minium) is required.
Effect of BPR and TDTA concentrations. At a T D T A con-
centration of 7.2 • 10 -4 M a BPR concentration in the range 4.2--
7.0 • 10 _5 M gave constant m a x i m u m absorbance.
With aluminium and BPR present in 1 : 3 molar ratio, and a low
T D T A concentration (2.4--5.9x10-SM), the ternary complex
58 C. Wyganowsky et ai.:

(~max=608 rim) is formed. This concentration range is below the

critical micelle concentration of TDTA and with increase in TDTA
concentration, the absorbance of the ternary complex increases 6.
When the molar ratio of TDTA to aluminium increases to 5--25,
the solution becomes turbid, probably because the ternary complex
precipitates (the reagent blank is transparent). When this molar
ratio reaches 36--57, the absorption m a x i m u m shifts to 623 nm
and the absorbance is m a x i m u m and constant. Further increase in
the molar ratio to 6 0 - - 1 2 0 decreases the absorbance. These results
indicate that various complexes are formed in the ternary system
as the TDTA concentration inreases. The absorption spectra of the
A 1 - - B P R - - T D T A complex for various TDTA conncentrations are
shown in Fig. 3. A 50-fold molar ratio of TDTA to aluminium
ensures formation of the ternary complex with m a x i m u m absorb-
ance at 2max= 623 rim.
Calibration graph and sensitivity. The calibration graph ob-
tained by the standard procedure was linear in the aluminium
range 0 . 1 - - 0 . 4 # g / m l and gave the molar absorptivity as 5.05 •

Table I. Molar Absorptivities for Aluminium-Bromopyrogallol Red-Quaternary

Ammonium Salt Systems at pH 4.7 and 50-fold molar Ratio of Quaternary Salt
to Aluminium

Quaternary ammonium salts )mlax~ n m 8~

1' mole-1.cm-1

Zephiramine . . . . . . . . . . . . . . . . . . . . . . . . . 623 4.5 x 104

Cetylpyridinium bromide (CP) . . . . . . . . . . 623 3.9 x 104
Trimethylstearylammonium chloride
(TSA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 618 3.5 x 104
Dodecyltrimethylammonium chloride
(DTA) . . . . . . . . . . . . . . . . . . . . . . . . . . . solutionturbid
n-Decyltrimethylammonium chloride
(n-DTA) . . . . . . . . . . . . . . . . . . . . . . . . . . 612 3.4 x 104
2,3,4-Triphenyltetrazolium chloride
(TPT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605 1.6 x 104
n- Octyltrimethylammonium bromide
(OTA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610 8.0 x 103

104 1.mole - 1 - c m -1. The molar absorptivities for other aluminium-

BPR-quaternary a m m o n i u m salt systems are shown in Table I.
Investigation of other quaternary a m m o n i u m salts showed that
all gave a bathochromic shift for the ternary complex, and that
 Spectrophotometric Determination of Aluminium 59

the sensitizing effect was strongly dependent on the length of the

hydrocarbon radical, increasing in the order T D T A > zephiramine >
CP > TSA > n-DTA > T P T > OTA.

0.8 08
2

0.7 07

0.6 0.5

0.5 0.5
i]" 't,.
8
g o.~ c0.4

.8
"~ 0.3 0.3

0.2 0.2

0.1 01

0 I I I I I ! I
4 5 6 7 550 600 650 700
pH Wavelength, hm

Fig. 2 Fig. 3

Fig. 2. Effect of pH at 623nm (CAl=l.48x10-SM, CBI,R=4.8xl0-SM,

CTDTA=7.2xl0-4M) of (1) BPR+TDTA measured against water; (2) AI-
BPR-TDTA complex measured against blank
Fig. 3. Absorption spectra of the A1-BPR-TDTA complex as a function of
TDTA concentration, CAI=1.48 x 10 -5 M, CBPR=4.2 x 10 -5 M; (1) CTDTA=
2.4x10 -SM, (2) 4x10 -SM, (3) 7.2x10 -4M, (4) 9.6x10 4M, (5) 1.4x10 -zM

Complex formation. Job's method of continuous variations and

the molar ratio method both showed that the aluminium-BPR ratio
was i : 2 in the presence of excess of T D T A (Figs. 4 and 5).
Effect of diverse ions. Bromopyrogallol Red reacts with many
ions, including iron, manganese, cobalt, nickel, copper, molyb-
denum(VI), vanadium, tungsten, zinc, silver, cadmium. The tolerance
limits for these and other ions was examined by the standard pro-
cedure and the results are shown in Table II. Certain ions would
not interfere when present at the concentrations usually found in
river water, since these are generally much smaller than the toler-
ance limits (taken as the levels causing 2% change in absorbance).
Iron interferes seriously, but can be masked with hydroxylammonium
60 C. Wyganowsky et a l . :

chloride and 1,10-phenanthroline. The method would not be suit-

able for hard waters (Ca > 80 rag/l).
Determination o~ aluminium in river water. River waters may
contain several forms of aluminium which do not react with
Bromopyrogallol Red, e. g. complexed or undissolved species. Thus,
when the total aluminium content is of interest, preliminary treat-
ment may be needed to convert all the aluminium into forms that
react with the reagent. Dougan and Wilson 8 reported the deter-

Table II. E f f e c t o f O t h e r Ions

Ion Concentra- Added as Absorbance*

tion ( M )

none 0.750
Na + 2 x 10 -a NaC1 0.750
K+ 2 • 10 - a KCI 0.750
C a 2+ 2 x 10 - a CaCI2 0.750
S r ~+ 2 x 10 -a SrC12 0.750
B a 2+ 1.2 x 10 - a BaCI= 0.745
M g 2+ 1.2 x 10 -a MgC12 0.755
C d 2+ 1.2 x 10 - a Cd(NOa)2 0.743
Co 2+ 2.8 • 10 - 4 CoCI~ 0.740
Sn 4+ 2.0 x 10 5 SnC14 0.742
Fe 2+ , Fe a + 2.0 x 10 - 5 FeCla 0.746**
Cr a+ 8.0 x 10 ~ CrCIa 0.752
N i ~+ 4.0 x 10 -5 Ni(NOa)~ 0.762
C u 2+ 4.0 x 10 -5 CuSO4 0.768
M n 2+ 4.0 x 10 -5 MnCh 0.760
Z n 2+ 4.0 x 10 -5 ZnSO4 0.742
T i 4+ i x 10 -5 Ti(804)2 0.767
V(V) 1 x 10 5 NH4VOa 0.768
Mo(VI) i x 10 - s Na~MoO4 0.768
NOa- 2.0 x 10-a NaNOa 0.750
C1- 2.0 x 10 -a NaC1 0.750
SO4 ~- 3.0 x 10 -a Na2SO4 0.750
HCOa 2.0 x 10 -a NaHCOa 0.746
Br- 8.0 x 10 - a NaBr 0.745
I- 8.0 x 10 - 4 NaI 0.750
SiOa 2- 6.0 x 10 - 4 Na2SiOa 0.761
C104- 3.0 x 10 - 5 NaC104 0.750
HPOa 2- 2.0 x 10 -6 Na2HPO4 0.750

* Reference: reagent b l a n k .
* * I r o n is masked with hydroxylammonium chlorideand 1,10-phenanthroline.
Concentrationof aluminium:1 . 4 8 x 10 -5 M .
 Spectrophotometric Determination of A l u m i n i u m 61

mination of aluminium in water with Catechol Violet, and tested

five preliminary treatments. Fuming with sulphuric acid, acidifying
with nitric acid or heating to boiling after acidification with hydro-

0.8

~7

0.6 ~5

0,5 ~5

0.4 }az

0.3
4:3

02 0,2

0.] Ol

! ! !
02 ad g6 0.8 10
%L/r%L+CspR) CBpR/~L

Fig. 4 Fig. 5

Fig. 4. C o m p o s i t i o nof the A1-BPR complex by Job's method (pH 5.5, ~,= 623 nm).
CTDTA=7.2x 10.4 M, CAI-}-CBPR= 1.48 x 10.4 M

Fig. 5. Determination of the molar ratio of BPR to a l u m i n i u m by the molar

ratio m e t h o d
(pH 5.5; CA1=7.4x 10 -a M, CBPR=7.4x 10.5 M, CTDTA=7.2x 10-4 M)

chloric acid gave almost the same values. In our work, all samples
were collected in polyethylene bottles containing sulphuric acid.
Three preliminary treatments were examined.
Treatment 1. T h e samples made 0.1 or 0.01 M in sulphuric acid
were analysed after filtration through a 0.45-#m membrane filter.
Treatment 2. T h e samples made 0.1 M in sulphuric acid were
analysed without further treatment.
Treatment 3. A 15-ml sample made 0.1 M in sulphuric acid, but
not filtered, was boiled for 10 min in a covered 50-ml beaker,
then cooled and analysed.
T h e results are given in Table III and indicate that all three
treatments gave satisfactory results. T h e recommended procedure
62 C. Wyganowsky et al.:

is as follows. Transfer up to 15 ml of sample (acidified with 5 ml

of concentrated sulphuric acid per litre), filtered or unfiltered, to a
50-ml beaker. Add 0.5 ml of 0.05 M hydroxylammonium chloride

Table III. Effect of Preliminary Treatment Methods on the Apparent A l u m i n i u m

Concentrations of Samples

Sample* Concentration o f a l u m i n i u m , #g/l

Treatment 1 Treatment 2 Treatment 3
A B A A

Asahi River I ......... 90 91 90 90

II . . . . . . . . . 80 82 82 84
III . . . . . . . . . 108 108 108 110
Yoshii River I ........ 87 88 89 88
II . . . . . . . . 81 81 81 80
III . . . . . . . . 111 113 113 115
T a k a h a s h i River I .... 79 80 80 80
II . . . . 78 80 80 82
III . . . . 80 80 82 82

A - - Samples 0.1 M in sulphuric acid.

B - - Samples 0.01 M in sulphuric acid.
* Symbols I--1II denote order of s a m p l i n g downstream. Sampled on Sep-
tember 9, 1981.

Table IV. Determination of A l u m i n i u m in River Water (sample volume 15 ml)

Sample Sampling date A l u m i n i u m content Recovery***

(#g/l)** (%)

Asahi River* I 28th April, 1981 92+3 103

II 28th April, 1981 92+4 104
III 28th April, 1981 86_+3 104
Potable water
(Okayama-shi) 24th April, 1981 125 + 3 104

* Symbols I--III denote order of sampling downstream.

.... The figures after the + signs are the standard deviations (6 determinations).
*** Tested with 2/~g of a l u m i n i u m added.

and mix well. After about 5 rain, add 1 ml of 0.01 M 1,10-phena-

throline and allow to stand for about 5 rain. Add 3 ml of 3.5 x 10-4M
Bromopyrogallol Red, 1 ml 0.016 M T D T A and 2 ml of buffer
solution (pH 5.5). Adjust the p H to 5.5 with dilute ammonia,
transfer to a 25-ml standard flask, dilute with water to the mark
and mix. Let stand for 10 rain and measure the absorbance at
 Spectrophotometric Determination of Aluminium 63

Table V. Comparison of Methods for the Spectrophotometric Getermination of

Aluminium whh Pyrogallol Red (PR), Bromopyrogallol Red (BPR) and
Other Reagents

Reagents Optimum 2max, n m e, Reference

pH 1.mole 1.cm 1

PR . . . . . . . . . . . . . . . . . 5.0+0.1 525 1.00• 7

BPR . . . . . . . . . . . . . . . 2.5 + 0.1 525 1.40 • 104 2
PR and CTA . . . . . . . . 6.8--7.2 610 4.80 x 104 1
BPR and Triton X-100 7.0 + 0.2 612 2.20 • 104 2
BPR and CTA . . . . . . 5.5 + 0.2 623 5.00 • 104 2
BPR and TDTA . . . . . 5.0--6.2 623 5.05 x 104 This work
Eriochrome Cyanine R 6.1--6.2 535 6.20 • 104 8
Stilbazo . . . . . . . . . . . . 6.8 520 3.80 x 104 9
Chrome Azurol S . . . . 5.8 568 2.15 x 104 10
Chrome Azurol S
and CTA . . . . . . . . . 5.8--6.0 620 1.08 • 105 11
Alizarin Red S . . . . . . 4.4--4.6 490 1.8 • 104 9

623 n m in a 1-cm glass cell against a reagent blank. The relative

standard deviation has been f o u n d to be less t h a n 5 % . The recovery
of a l u m i n i u m has been tested by adding k n o w n a m o u n t s of alu-
m i n i u m to the sample solutions (Table IV).

Conclusions
The m e t h o d proposed can be applied to determination of micro
a m o u n t s of a l u m i n i u m in natural waters with satisfactory results.
Table V compares this m e t h o d with several others for spectrophoto-
metric determination of a l u m i n i u m . The sensitivity of the m e t h o d
is lower than that of the m e t h o d s using Eriochrome Cyanine R or
C h r o m e Azurol S in the presence of a c e t y l t r i m e t h y l a m m o n i u m
salt, but has some advantages, such as relatively high sensitivity,
a relatively simpler and less time-consuming procedure, good repro-
ducibility and wide p H range for complex f o r m a t i o n

Summary
Spectrophotometric Determination o[ Aluminium with Bromopyro-
gallol Red and a Quaternary Ammonium Salt: Determination o[
Aluminium in River Water
In the presence of n - t e t r a d e c y l t r i m e t h y l a m m o n i u m bromide
a l u m i n i u m reacts with Bromopyrogallol Red (BPR) to f o r m a ter-
nary complex, in which the m o l a r ratio of a l u m i n i u m ot BPR is
64 C. Wyganowski et al.: Determination of Aluminium

1 : 2 . T h e method is suitable for the determination of traces of

aluminium in natural waters. T h e ternary complex has an absorb-
ance m a x i m u m at 623 m m with molar absorptivity 5.05 x 1041.
m o l e - l . c m -1. Beer's law is obeyed over the range 0.1--0.4#g/ml
of aluminium. Iron(II) and iron(III) interfere but can be masked
with hydroxylammonium chloride and 1,10-phenanthroline. Alu-
m i n i u m can be determined at about the 100-/~g/1 level in river water.

Zusammenfassung
Spektrophotometrische Bestimmung von Aluminium in FIuflwasser mit
Brompyrogallol-Rot und einem quaterndren Ammoniumsalz
In Gegenwart von n-Tetradecyltrimethylammoniumbromid reagiert
Aluminium mit Brompyrogallolrot (BPR) unter Bildung eines tern~iren
Komplexes im Verh~iltnis 1 : 2 (AI : BPR). Das Verfahren eignet sich for
die Bestimmung yon Aluminium in natiirlichen W~issern. Die Absorbanz
des Komplexes bei 623 nm betr~igt 5.05 x l041.mol 1.cm-L Bei 0.1--
0.4#g A1/ml wird das Beersche Gesetz erfiillt. Eisen(II) und (III) st6ren
zwar, lassen sich abet mit Hydroxylammoniumchlorid und 1,10-Phenan-
throlin maskieren. In Flugwasser kann A1 in der Gr6genordnung 100/~g/1
bestimmt werden.

References
1 C. Wyganowski, Microchem. J. 26, 45 (1981).
2 C. Wyganowski and M. Kolczynska, Microchem. J. 27, 37 (1982).
a T. Korenaga, S. Motomizu, and K. T6ei, Talanta 27, 33 (1980).
4 T. Korenaga, S. Motomizu, and K. T6ei, Analyst 105, 328 (1980).
5 T. Korenaga, S. Motomizu, and K. T6ei, Analyt. Chim. Acta 104,
369 (1979).
6 S. B. Savvin, R. K. Chernova, and G.M. Beloliptsera, Zh. Analit.
Khim. 35, 1128 (1980).
v T. Tanaka, Y. Nakagawa, and S. Honda, Bunseki Kagaku 10,
1148 (1961).
8 W. K. Dougan and A. L. Wilson, Analyst 99, 413 (1974).
9 j. A. Corbett and B. D. Guerin, Analyst 91, 490 (1966).
10 p. Pakalns, Analyt. Chim. Acta 32, 57 (1965).
11 y. Shijo and T. Takeuchi, Bunseki Kagaku 17, 61 (1968).

Correspondence and reprints: C. Wyganowski, Institute of General

Chemistry, Technical University, 90-924 L6dz, Poland.