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Separation of Chromium (III) and Chromium (VI) by Ion Chromatography
Separation of Chromium (III) and Chromium (VI) by Ion Chromatography
Separation of Chromium (III) and Chromium (VI) by Ion Chromatography
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of 5 to 15 mg/L. Higher amounts of nitric acid (e.g. 50
µL) resulted in greater preservation of Cr(III) but caused
a loss of Cr(VI). Reducing the heating time from 30 min
may reduce Cr(III) loss. A one min heating time was
–50
0 2 4 6 8 inadequate for Cr(III)-PDCA complex formation, but for
Minutes
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Absorbance (mAU)
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was used to measure the amount of Cr(VI) formed from
duplicate preparations of a 15 mg/L Cr(III) standard.
As shown in Table 1, 1.24 mg/L Cr(VI) was produced
from 15 mg/L Cr(III), which represents an 8.27%
conversion of Cr(III). Three mixed standards were then –50
0 2 4 6 8
prepared with the concentrations listed in Table 2; their Minutes 25478
chromatography is also shown in Figure 2. The third row Figure 4. Overlay of chromatograms of Cr(VI) standards: 0.25,
of Table 2, (Cr(VI) Total), reflects the predicted amount 0.5 and 0.75 mg/L, respectively.
of Cr(VI) from the amount added and the amount derived
from Cr(III). Calibrations were linear for both oxidation
states with correlation coefficients of 0.9999 and 0.9998,
respectively. To ascertain the accuracy of this approach, Table 1. Determination of the Amount of Cr(VI)
in the 15 mg/L Cr(III) Standard
a mixed standard was analyzed with added concentrations
Number Area Height Amount
of Cr(III) and Cr(VI) of 15 and 0.5 mg/L respectively.
mAU/min mAU Cr(VI)
Due to the expected conversion of some of the Cr(III) to (mg/L)
yield an additional 1.24 mg/L, the authors expected a total 1 16.98 81.69 1.24
of 1.99 mg/L Cr(VI). The measured values for Cr(III) and 2 16.97 81.55 1.24
Cr(VI) were 15.0 mg/L and 1.99 mg/L.
Average: 16.97 81.62 1.24
Determination of Cr(III) and Cr(VI) in Soil and Wastewater
To determine the feasibility of this method for
speciation of chromium in soil and wastewater samples,
Table 2. Mixed Standard Concentrations
the authors spiked known quantities of a mixed standard
Analyte Concentration (mg/L)
into samples that contained no measurable amounts
of chromium. Samples spiked with standards and Level 1 Level 2 Level 3
unspiked samples were treated with 50 mM nitric acid Cr(III) 5.0 10.0 15.0
to approximate the manner in which the standards were Cr(VI) 0.25 0.5 0.75
treated, and followed by immediate addition of the 10× Cr(VI) Total* 0.66 1.32 1.99
eluent concentrate buffered at pH 6.8. In reference 5, the *This value reflects the amount of Cr(VI) added and the amount expected from Cr(III) oxidation.
authors extracted soil using phosphate buffer at the pH
of the suspended soil sample to efficiently extract Cr(VI)
from the soil. In this method, the authors did not attempt
this type of extraction, as pH values significantly different
from 6.8 may interfere with production of the Cr(III)-
PDCA complex.
Absorbance (mAU)
soil and wastewater samples to avoid contaminating the
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CS5A column. Figures 5 and 6 each show an overlay of
chromatograms of the soil or wastewater sample and the
same sample spiked with a mixed Cr(III)/Cr(VI) standard.
Both samples contain no measurable chromium. Tables –50
0 2 4 6 8
3 and 4 show recovery of Cr(III) and Cr(VI) from both Minutes
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samples. The recovery calculations assume an 8.27% loss
Figure 5. Overlay of the chromatograms of the soil sample and
of Cr(III) and concomitant production of Cr(VI) during the same sample spiked with 10 mg/L Cr(III) and 0.5 mg/L Cr(VI).
sample preparation, as measured in the experiments
described earlier. This method allows an estimation
of the Cr(III) and Cr(VI) amounts in each sample in a Column: IonPac CS5A + CG5A (4 mm) Inj. Volume: 50 µL
Eluent: 2 mM PDCA, 2 mM Na2HPO4, Detection: 0.0–4.7 min, UV 335 nm
single injection. For an accurate measure of the sample 10 mM NaI, 50 mM CH3CO2NH4, 4.7–8.0 min, Visible 530 nm
concentration of Cr(VI), the authors recommend the 2.8 mM LiOH Chromatogram: 1. Wastewater sample
Flow Rate: 1.0 mL/min 2. Spiked wastewater sample
method described in Dionex Application Update 144. For
120 Peaks: 1. Cr(III) 10.56 mg/L
a measure of total chromium, samples can be oxidized 2. Cr(VI) 1.26
with ammonium persulfate then measured using the
2
method in AU144. Cr(III) concentration can be derived
Absorbance (mAU)
Table 3. Recovery of 10 mg/L Cr(III) and 0.5 mg/L Table 4. Recovery of 10 mg/L Cr(III) and 0.5 mg/L
Cr(VI) in a Soil Sample Cr(VI) in a Wastewater Sample
Sample No. Amount (mg/L) Sample No. Amount (mg/L)