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SPECTROPHOTOMETRIC DETERMINATION OF LEAD

WITH l -(2-PY RIDY LAZO)-2-NAPHTHOL AND
NON-IONIC SURFACTANTS

APPLICATION TO ACETIC ACID EXTRACTS

OF CERAMIC ENAMELS

J. MEDINA ESCRICHE, M. LLOBAT ESTELLESand A. SEVILLANOCABEZA

Department of Analytical Chemistry, Faculty of Chemical Sciences, Valencia Umversity. Buqasot.
Valenaa. Spain

(Received 24 November 1984. Revised 24 May 1985 Accepted 14 June 1985)

Summary-The Pb-PAN system in the presence of non-ionic surfactants (polyoxyethylene nonylphenols)

has been studied spectrophotometrically. The optimum conditions for Pb determination are pH 9
(Na:B,O,-HCIO,), 5% surfactant and measurement at 555 nm. The system obeys the Ldmbert Beer law
over the Pb concentration range I .34.5 ppm; the molar absorpttvtty IS 2.02 x IO” I.mole ‘cm ’ at 555 nm
The relattve standard deviation IS 0.9% and the limit of detection 0.12 ppm. Lead can be determmed in
acetic acid extracts of ceramic enamels by extraction wtth sodium diethyldtthiocarbamate into carbon
tetrachloride and stripping with 4M hydrochloric actd to remove interferent species. The results obtained
are in agreement with those obtained by a standard AAS method.

PAN is widely used as a calorimetric reagent for RESULTS AND DISCUSSION

metals. Its metal complexes are generally only slightly
soluble in water, so extraction methods are generally Pb-Nemo1 Kl030-PAN system
used. An alternative is to use surfactants as solu- Infhence of pH. The spectra of PbPAN solutions
bilizing agents,‘.* e.g., Triton X- 100 in determination in presence of Nemo1 K1030 at different acidities,
of Co, Ni, Mn and Zn and of NEMOL K1030 for ionic strength 0.1 M and temperature 25, measured
determination of Cd.3-7 A methanolic medium has against reagent blanks (Fig. 1) show an absorption
been used for determination of Pb with PAN.’ band with a maximum at 555 nm, increasing in
intensity with pH, to a maximum at pH l&11
EXPERIMENTAL (Fig. 2). At pH < 9 the absorbance at 555 nm is stable
for at least 30 min, but at higher pH the absorbance,
Reagents
Stock solution (1000 pg/ml) of lead nitrate.
Stock 5 x IO-‘M solution of o-PAN in methanol.
Stock 25% solution of Nemo1 K1030 (Masso-Carol) with
hydrophile-lipophile balance 15.1.
Procedure
Stand 2 g of sample in 50 ml of 4% v/v acetic acid for
24 hr at room temperature, then filter into a IOO-ml standard 04
flask and dilute to volume with 4% v/v acetic acid. To 20 ml
of this solution add 5 ml of 20% sodium citrate solution,
20 ml of 2.5M ammonia/2.5M ammonium chloride buffer, T
5 ml of 0.5% sodium diethyldithiocarbamate solution and
10 ml of carbon tetrachloride, shake the mixture for 5 min.
then separate the phases, shake the organic phase with 02
IO ml of I M ammonia/ 1M ammonium chloride solution for
5 min. and discard the aqueous phase. Then strip the lead
by shaking the organic phase with 10 ml of 4M hydrochloric
acid for 5 min and separate the phases. Dilute the aqueous
phase to volume m a 25-ml standard flask with demin-
eralized water. Neutralize a suitable volume of this solution
wtth sodium hydroxide solutton, add 5 ml of 25% Nemo1
K1030 solution, 5 ml of 5 x IO-‘M PAN and 10 ml of 4M X(ml)
ammonia/4M ammonium chloride buffer, and dilute to the Fig. 1. Influence of pH on the absorption spectra of the
mark in a 25-ml standard flask with demmeralized water. Pb-Nemo1 K1030-PAN complex. pH: I, 5.9; 2, 6.7; 3, 8.2;
Measure the absorbance at 555 nm (m 2-cm cells) agamst a 4, 9.3; 5. 10.2: 6, 10.7; Pb (II) 2 ppm. Nemo1 K1030 5%,
reagent blank prepared in the same way. PAN IO-‘M.

058
 SHORT COMMUNlCAnONS 1059

Table I. Influence of Cd on determmation of Pb

in presence of NH,’ ,‘NH, buffer solution
05-
Absorbance at 555 nm
Pb (p/w) Cd absent I ppm Cd 2 ppm Cd
0.55 0.05 I 0.049 0.054
vo3- 109 0.120 0 IIX 0.125
2.19 0 227 0.225 0 ‘37
3 28 0.350 0 339 0.354
4.37 0.460 0.44X 0 466
0.1 -

Elimination of’ interfrrents. The selectivity of the

6 6 10 12 method is improved by extraction with sodium di-
PH
ethyldithiocarbamate and carbon tetrachloride’ and
Fig. 2. Absorbance us. pH for PbNemol K1030-PAN at
scrubbing with ammonia buffer to remove inter-
555 nm. Reference reagent blank.
ferences. The lead is then quantitatively stripped with
10 ml of 4M hydrochloric acid. Lead can be deter-
though higher, decreases slowly with time (Fig. 3). A mined in the presence of l-2 ppm cadmium in 4M
pH of 9 is therefore chosen as the optimum working ammonia buffer (Table 1).
PH. Precision and limit qf‘ detection. Analysis of six
Injkence of surfactant concentration. A final surfac- independent solutions containing 20 ppm each of
tant concentration lower than 2% does not prevent cadmium, lead and zinc showed that the relative
appearance of a precipitate in a 2-ppm lead solution standard deviation of the lead determination is I .3”,;,
with 10-3M PAN at pH 9. but higher surfactant which compares favourably with the corresponding
concentrations give red solutions. The presence of values of 2% and 1.1% obtained for AAS mea-
2-S% Nemo1 K1030 makes the absorbance of surement at 217 and 283.3 nm, respectively (for 10
PbPAN solutions and PAN blanks stable for at least ppm of lead).
30 min and 5% surfactant concentration is chosen as
the most suitable. Determination of Pb(lI) in acetic acid extracts of
Infiuence of PAN concentration. Varying the PAN ceramic enamels
concentration with a fixed concentration of lead Five industrial samples of ceramic enamels of
(lo-‘M) and of Nemo1 K1030 (5%) at pH 9 shows different composition, supplied by Ferroenamel
that a [PAN]/[Pb] ratio of at least 100 is needed to Espaiiola were analysed in triplicate by the proposed
produce an absorbance that is practically indepen- method and the results are shown in Table 2.
dent of the PAN concentration. The values obtained were generally within 5% of
Analytical characteristics. The system obeys the those obtained by application of the standard AAS
Lambert-Beer law over the lead concentration range method” to the initial acetic acid solutions.
1.34.5 ppm; the molar absorptivity is 2.02 x 10’ A 1-test”-‘3 shows that the method has no system-
I. mole-‘. cm-’ at 555 nm. The relative standard devi- atic error and does not need a blank correction.
ation (s,) of the absorbance for 10 independent tests
is 0.9% and the limit of detection (cL) is 0.12 ppm Pb Table 2. Pb contents of acetic acid extracts
(cL is defined’ as the concentration giving a signal of ceramic enamels obtained by the pro-
equal to three times the standard deviation of the posed method and by AAS
blank signal). Pb, ppm
AAS Proposed method

0.5 Sample X, R, X, x, -
49.5 51.9
1 49.3 49.4 51.5 51.6
49.5 51.3
11.2 14.4
2 11.1 11.3 14.4 14.5
T 0.4
11.5 14.6
16.1 16.6
3 15.6 16.1 17.2 16.9
b
16.6 16.8

0.j L--
L I I I
4
8.4
8.3
8.4
8.4
8.5
8.8
8.8
8.7
30 60 90
t (mm) 27.6 26.2
Fig. 3. Stability as a function of pH for Pb-Nemo1 5 27.3 27.7 26.0 26.4
K1030-PAN solutions, pH: 1, 8.2; 2, 9.3; 3, 10.2; 4, 10.7. 28.2 26.9
1060 SHORT COMMUNICATIONS

Table 3. Cd contents of acetic acid extracts under identical conditions. Comparison of the results
of ceramic enamels, obtained by the pro- (Table 3) with those obtained by AAS shows a
posed method and by AAS difference of less than 57; and a t-test shows there is
Cd. ppnl no systematic error and that a blank correction is not
AAS Proposed method needed.
Sample X, R,- X, 8, authors thank Ferroenamel
Acknowledgements-The
36.0 35.0 Espaiiola, Almazora, CastelIon. Spam for collaboration and
1 36.5 35.8 35.5 35.4 the supply of the ceramic enamels used in the work.
35.0 35.6
14.1 14.6
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2 14.0 14.1 14.2 14.2
14.1 13.7 1. K. Ueno, m MTP Intern. Rrr. Sci. Phys Chem. Ser.
3 - One: Anal. Chem.. 1973. 13, 43.
2. W. L. Hinzer. in Solution Chemrslry of Surfactunrs.
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4 6.3 6.1 6.3 6.4 New York, 1979.
6.1 6.5 3. H. Watanabe, Talunfa, 1974, 21, 295.
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752.
6. H. Watanabe, Bunseki Kagaku, 1974, 23, 396; Chem.
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Cadmium can also be determined in the 4M hydro- I. J. Medina Escriche, M. Llobat Estelles and F. Bosch
chloric acid solution in stripping the lead.
obtained Reig, Tulanfa, 1983, 30, 915.
8. D. Negoui, A. Knza and L. Baldue. Anul. Unrc.
An aliquot of this solution is neutralized with sodium
Bucuresti Ser. Stunt. Nat.. 1964, 13, 165.
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lo-’ M PAN and 10 ml of borate-perchloric acid 10. ASTM C 738-76.
11. J. Mandel and F. J. Lmning, Anal. Chem.. 1957,29,743.
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12. Comisariat a I’Energie Atomique. Star&&e uppbqueh
to the mark in a 25ml standard flask with demin- a I’exploitarion de mesures, Masson, Paris, 1978.
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555 nm and 25” against a PAN blank prepared Qulm., 1981. 77, 129.