Beruflich Dokumente
Kultur Dokumente
Received 28 August 1997; received in revised form 1 September 1997; accepted 17 September 1997
Abstract
A standard additions method in ¯ow injection atomic absorption analysis has been described. The proposed method was
applied to the determination of calcium in synthetic samples with and without chemical interference and the results were
compared with those obtained by the conventional standard additions method in atomic absorption spectrometry. The
in¯uence of parameters of the ¯ow injection system was studied. The results showed that the proposed method was
independent of such parameters. The relative standard deviations within and between analyses were found to be 1.61 and
1.81%, respectively, at the 1.5 mg mlÿ1 Ca level. The method was used for the determination of calcium in tap water. # 1997
Elsevier Science B.V.
pointed out that most of the drawbacks of the manual atomic absorption analysis. The idea of the proposed
method are minimized in an FI system, which always method is based on the `compensation method'
yield highly precise measurements after rapid proces- [15], in which the pumping rate is less than the
sing of small sample volumes. Different ¯ow injection nebulization rate. The standard solutions are injected
methods [3] have been proposed for calibration by a via a rotary valve into the carrier stream of water, and
SAM; the sample solution is sucked by the compensation
branch. The ¯ow rate of the compensation branch is
1.1. Merging zone just suf®cient to compensate the ¯ow rate of carrier
stream and so the nebulization rate is steadily kept
The simplest form of a merging zone SAM mani- constant.
fold was used by Zagatto et al. [4]. The method was
applied for the determination of Cu, Ni and Zn by the
so-called `generalized SAM', which compensates for 2. Experimental
both matrix and spectral interferences, in conjunction
with inductively coupled plasma atomic emission 2.1. Apparatus
spectrometry (ICP-AES). In order to vary the concen-
tration of standard, a zone sampling manifold was A Unicam SP9 atomic absorption spectrometer and
combined with the merging zone principle by Gine et a Perkin±Elmer R100 recorder were employed. The
al. [5]. The manifold was again used for the imple- atomic absorption spectrometer was operated as
mentation of the generalized SAM, this time for the recommended by the manufacturer for maximum
determination of 19 elements in rock samples by ICP- sensitivity with an acetylene/nitrous oxide ¯ame. A
AES [6]. Desaga PLG±Peristaltic pump with Desaga silicone
tubing E, Rheodyne PTFE rotary valve type 50 and
1.2. Reagent injection FIA Supelco PTFE tubing (0.5 mm i.d.) with couplings
were used in the FI system.
The simplest version of this method (a single line
manifold) was ®rst described by Tyson [7] and has 2.2. Reagents
been used for the determination of Ca in iron ore [8],
Cr in steel [6], Mg in aluminate [9], Ca in cement [10], The stock standard solution of calcium (1000 mg
Si in phosphoric acid [11], and Ba and Cr in river mlÿ1) was prepared by dissolving 0.5892 g of
sediment and coal ¯y ash [12]. In this technique, the Ca(NO3)24H2O (Fluka, purum p.a.) in 100 ml of
sample is used as the carrier stream and standards are triply distilled water. The working standard calcium
injected. A merging stream version of the method has solutions were prepared by appropriate dilution of the
been described by Araujo et al. [13] for the determi- stock solution with the pure water. The stock solution
nation of Na, K and Ca by ¯ame AES. of sodium (50 mg mlÿ1) as the chemical interference
was prepared by dissolving 18.4849 g of NaNO3
1.3. Zone penetration method (Merck, zur analyse) in 100 ml of triply distilled
water.
Fang et al. [14] used the manifold which produced The sample solutions without interference were
an analyte solution zone sandwiched between water prepared by taking known volumes of standard cal-
(in front) and standard (at the rear). Based on the cium solutions and diluting to the appropriate volume
overlapping zone, it is possible to calculate the con- with water. The sample solutions with chemical inter-
centration of the standard at a point of known disper- ference were prepared by mixing known volumes of
sion coef®cient of the sample. The concentration of standard calcium and sodium solutions. The concen-
sample can be calculated from the concentration of tration of sodium in sample solutions with chemical
standard. interference was kept constant at 2000 mg mlÿ1. Tri-
The main purpose of this paper is to introduce a ply distilled water was used in all experiments as the
method for standard additions in ¯ow injection carrier stream.
B. Haghighi et al. / Analytica Chimica Acta 357 (1997) 151±156 153
Fig. 1. Manifold of the standard additions method in flow injection atomic absorption spectrometry. P, pump; I, injection valve; C1 and C2,
mixing coils; T, three-way connector; AAS, atomic absorption spectrometer; Vs, flow rate of carrier solution; Vx, flow rate of compensation
branch; Vn, nebulization rate.
2.3. Manifold procedure and mathematical concepts rotary valve. The response is shown as X in Fig. 2.
In the second stage, sample solution is used as eluent
The manifold based on the compensation method from the compensation branch, the ¯ow rate of which
was used and is shown in Fig. 1. The calibration is Vx. The steady state response to this is shown as Y in
procedure is performed in three stages. At ®rst, water Fig. 2. The total ¯ow rate into the nebulizer Vn ( Vs
is used as carrier and compensation eluent. The ¯ow Vx) is steadily kept constant, and thus as Vs is
rate of carrier stream is adjusted to Vs, which is less increased, Vx is decreased and vice versa. In the last
than the aspiration rate of the nebulizer (Vn). Sample stage, while water is used as carrier and sample as
solution with concentration Cx is injected via the compensation eluent, a standard solution with con-
Fig. 2. Typical recorder trace of the proposed standard additions method. For details see text.
154 B. Haghighi et al. / Analytica Chimica Acta 357 (1997) 151±156
centration Cs is injected via the rotary valve. The results were investigated. Details of these studies are
transient response to this is shown as S in Fig. 2. presented in the following section.
From a mathematical point of view, in an instrument
such as an atomic absorption spectrometer [1], the 3.1. Effect of flow rate of carrier solution
response signal (R) is linearly related to the concen-
tration of species of interest: As was noted before, Vx is a function of Vs, while Vn
is constant. Three levels of Vs were chosen, in which
R kC
VsVx (approximately), Vs>Vx and Vs<Vx. The in¯u-
in which k is the constant of proportionality. So, in the ence of Vs on the results was investigated. The results,
similar manner, which are summarized in Table 1, show that at any Vs,
kCx Vs kCx Vx while Vs<Vn, the proposed method is in good agree-
X ; Y ment with the conventional SAM, and the proposed
DVn Vn
method is independent of Vs or Vx.
;in which D is the diffusion coef®cient of the species
through the ®rst and second mixing coils. The plot of 3.2. Effect of lengths of mixing coils C1 and C2
signal (S) vs. Cs yields the calibration equation with a
slope of kVs/DVn and intercept of kCxVx/Vn, i.e. Mixing coil C1 is used to damp the shock caused by
Cs Vs Cx Vx the injection valve and mixing coil C2 is used to
S k
: improve the mixing of standard and sample solutions.
DVn Vn
In addition to this effect, the dispersion coef®cient is
Therefore, X SlopeCx and Cx Slopeÿ1X. affected by the change of the lengths of C1 and C2. The
effect of the lengths of C1 and C2 on the results were
3. Results and discussion studied and summarized in Table 2. The results of the
proposed method are in good agreement with the
The concentrations of calcium of a series of work- results of a conventional SAM and independent of
ing solutions were determined by the proposed the lengths of C1 and C2.
method and the results were compared with the results
of a conventional SAM (an ordinary standard addition 3.3. Effect of sample volume
procedure without using a ¯ow system) by AAS. In
these studies, the in¯uence of parameters of the FI The in¯uence of sample volume on the results of the
system such as the ¯ow rate of the carrier stream, proposed method was investigated and is summarized
length of the mixing coils and sample volume on the in Table 3. The results of the proposed method are
Table 1
Influence of flow rates of carrier solution on the results for determination of calcium with and without chemical interference by the proposed
method and comparison with the results of a conventional standard additions method (CSAM) by atomic absorption analysis. Conditions; C1,
50 cm; C2, 30 cm; sample volume, 200 ml; Vn, ca. 6.4 ml minÿ1
Table 2 Table 3
Influence of lengths of mixing coils C1 and C2 on the results of Influence of sample volume on the results of determination of
determination of calcium with and without chemical interference calcium with and without chemical interference by the proposed
by the proposed method. Conditions; C2, 30 cm (for studying the method. Conditions; C1, 25 cm; C2, 15 cm; Vs, 3.2 ml minÿ1
effect of C1); C1, 25 cm (for studying the effect of C2); sample
volume, 200 ml; Vs, 3.2 ml minÿ1 Sample volume (ml) mg mlÿ1 Ca
Table 4
Results of water samples analyses by the proposed method and the conventional standard additions method (CSAM) by atomic absorption
analysis. Conditions; C1, 25 cm; C2, 15 cm; sample volume, 50 ml; Vs, 3.2 ml minÿ1
advantageous with respect to some of the other SAMs [6] J.F. Tyson, A.B. Idris, Analyst 109 (1984) 23.
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[8] J.F. Tyson, A.B. Idris, Analyst 106 (1981) 1125.
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