Determining Ni With Dimethylglyoxime
Determining Ni With Dimethylglyoxime
Determining Ni With Dimethylglyoxime
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Article ID 1005-9040(2007) -04-39945 ScienceDirect
A novel method for the determination of nickel and palladium in environmental samples by low temperature ETV-
ICP-OES with dimethylglyoxime( DMG) as both the extractant and chemical modifier has been developed. In this
study, it was found that nickel and palladium can form complexes with dimethylglyoxime(0.05% , mass fraction) at
pH 6.0 and can be extracted into chloroform quantitatively. The complexes can be evaporated into plasma at a suita-
ble temperature( 1400 'I:) for ICP-OES detection. Under the optimized conditions, the detection limits of nickel and
palladium are 0. 48 and 0.40 ng/mL, respectively, while the RSD values are separately 5.0% and 3. 1% ( p = 50
ng/mL, n = 7 ) . The proposed method was applied to the determination of the target analytes in environmental sam-
ples with satisfactory results.
Keywords Low temperature electrothermal vaporization ; ICP-OES ; Dimethylglyoxime; Chemical modifier ; Nickel
and palladium
fect the formation and extraction of the complexes and 1.0% (mass fraction) dimethylglyoxime were added in-
the chemical modification of dimethylglyoxime were to a centrifugal flask and diluted to 10 mL. The mixture
studied. The method developed was applied to the de- was allowed to react for 10 min at mom temperature,
termination of environmental samples and satisfactory which was followed by the addition of 2 mL of chloro-
results were obtained. form. The mixture was sonicated for 10 min and centri-
Experimental fuged at a speed of 3500 r/s for 3 min after which the
1 Apparatus water phase was discarded. The organic phase of 10 pL
The pieces of apparatus used included: a high fre- of the solution was injected into the graphite furnace af-
*
quency ICP source [ 2 kW, ( 27 3 ) MHz, Beijing ter the ignition and stabilization of ICP. Under the
Broadcast Instrument Factory, China ] , a WDG-500- heating cycle, the analyte was evaporated into the plas-
1A type monochromator ( Beijing Second Optics, Chi- ma to determine the height of the signal peak.
na) , a WF-1C type heated device with a WF4C type Results and Discussion
graphite furnace ( Beijing Rayleigh Analytical Instru- 1 Vaporization Behavior of Ni And Pdz*
ment Corp. , China), a WR456 type photomultiplier The complexes of NiZ and Pd2+ with dimethylg-
tube ( Hamamatsu, Japan) , and a U-135C recorder lyoxime are thermally stable and volatile, which can
( Shimadzu , Kyoto, Japan ) . A WX-3000 microwave completely sublime under vacuum at a temperature
accelerated reaction system was also used( Shanghai EU higher than 100 T,These characteristics of both com-
Chemical Instruments Co. , Ltd. , China). The opera- plexes are utilized to vaporize and transport the ele-
tional parameters are shown in Table 1. ments of interest into ICP for determination. Fig. 1
Table 1 Operational parameters of ETV-ICP-OES shows the signal profiles of nickel and palladium deter-
Wavelength/nm Pd 340.3, Ni 341.4 mined by ETV-ICP-OES. It can be observed that in the
Power/kW 2.0
presence of dimethylglyoxime, nickel and palladium
Canier gas flow rate/(L * min-I) 0.6
can be completely evaporated at 1400 T [ Fig. 1 ( A ) 3
Coolant gas flow rate/( L * min-l ) 16
Plasma gas flow rate/( L min )- 0.8 and a sharp signal peak can be obtained. No obvious
Observation heighvmm 12 memory signal is observed in the cleaning step at
Drying temperature/% SO( ramp 15 s, hold 30 s) 2600 c [ Fig. 1 ( B) 1. On the contrary, weaker and
Vaporization temperature/C 1m(ramp 0 s, hold 5 s) wider signal peaks are observed in the absence of dime-
Cleaning temperatudC 2500(rampO hold4 a )
8,
thylglyoxime[ Fig. 1 ( C ) ] at 2500 r: and obvious me-
Sample volume/bL 10
mory signal can be observed at 2600 C [ Fig. 1 ( D ) ].
2 Reagents
Stock standard solutions of Ni2+( 1 mg/mL) and
Pd2+ ( 1 mg /mL) were prepared via standard me-
thods. The standard working solutions were prepared by
stepwise dilution of the stock standard solutions. Dime-
thylglyoxime( A. R. ) was purchased from Beijing Insti-
tute of Chemical Reagents and was prepared into a
1.0% ( mass fraction) solution in ethanol. The pH of
analytical solution was adjusted with a 0. 1 moVL 5s
NaOH-KH,PO, buffer solution. Other reagents used in -
11s
the experiments were of analytical reagent grade. Dou-
bly distilled water was used all through. Fig. 1 Signal profdes of nickel and palladium
( A ) Evaporated at 1800 qC ; ( C ) evaporated at 2500 9: ; ( B ) and
Artificial seawater was prepared by following the ( D ) cleaningat2600qC;p(NiZ*) a n d p ( P d z + ) : 20ng/mLfor
method reported in ref. [ 17 ] : 0.3675 g of CaC1, ( A ) and ( B ) ; 1 PdmLfor ( C ) and ( D ) .
2 H z 0 , 3.275 g of MgSO, 7H,O, and 6.975 g of The effect of temperature on the vaporization be-
NaCl.were dissolved in 250 mL doubly distilled water. havior of an analyte was optimized for further study.
Lake water sample was collected from the East Lake of The sample was injected into the graphite furnace and
Wuhan , China. dried at 100 C to remove the solvent. After that, the
3 General Procedures signal intensities were recorded at various tempera-
Solution of 2 . 0 mL of 100 ng/mL NiZ or Pd2+, +
tures. The results shown in Fig. 2 indicate that nickel
1 . 0 mL of NaOH-KH,PO, buffer, and 0.5 mL of and palladium can be evaporated at 800 r: in the pre-
No. 4 PAN Liang et al. 40 1
sence of dimethylgloxime( Fig. 2 curve u ) . With the in- be extracted with chloroform quantitatively. Therefore,
crease in vaporization temperature, the signal intensi- pH 6.0 was selected for subsequent analysis.
ties also increase gradually. When the vaporization
temperature is higher than 1400 T , the signal intensi-
ties reach the maximum and remain constant, which in-
dicates that nickel and palladium are evaporated com-
pletely. On the other hand, without dimethylglyoxime
( Fig. 2 curve b ) , the signal intensities increase gradu-
ally as the temperature is increased up to 2500 T and
no plateau can be found in the vaporization curves,
4.0 5.0 6.0 70 8.0
which indicate that nickel and palladium cannot be
PH
evaporated quantitatively at a temperature lower than
Fig.3 Effect of pH
2500 T .
p( NiZ+) =20 ng/mL; p ( Pd2+) =20 ng/mL.
B
a
i
z
0.21
0.0 I
d a
I I I I I
plexes completely if the mass fraction of chelating rea-
gent is extremely low.
It is shown in Fig. 4 that the signal intensities of
600 1000 1400 1800 2200 2600 nickel and palladium vary along with the mass fraction
1/% of dimethylglyoxime. With increasing mass fraction of
Fig. 2 Effect of vaporization temperature on signel in- dimethylglyoxime, the signals of nickel and palladium
tensity are gradually enhanced. When the mass fraction rea-
a. With dimethylglyoxime [ p ( Ni2 ) = p ( Pd2 ) = 20
ches 0.03% , the signal intensities approach the maxi-
+ +
to 100, the organic phase cannot be recovered quantita- and palladium, respectively. The relative coefficients
tively because of the dissolution of chloroform in water are 0. 99676 and 0. 99673, respectively. It is noticed
and diflicult phase separation. Therefore, the volume that the calibration curves deviate from the origin espe-
ratio of water to chloroform was selected to be 50: 1. cially that of palladium. This deviation is probably
5 Effect of Coexisting Ion caused by the deposition of palladium complexes in the
In the analyses of real samples, abundant coexis- transmission procedure. The detection limits that were
ting ions will probably influence the determination of calculated to be three times the standard deviation of
concerned elements. Therefore, solutions of 50 ng/mL the reagent blank signal( n = 7 ) in accordance with IU-
Ni2' and PdZ+containing the most abundant ions in en- PAC recommendations are 0.48 ng/mL for nickel and
vironmental samples including K' , Na' , Ca2' , and 0.40 ng/mL for palladium. The relative standard devi-
M i + etc. were prepared, extracted, and determined ation is 5.0% for nickel and 3. l % for palladium
according to the aforementioned procedure. The tole- [p(NiZ') a n d p ( P d Z ' ) : 20 ng/mL, n = 5 ] .
rance limits of coexisting ions within which the coexis- Environmental Sample Analysis
ting ions do not interfere with the determinations of tar- 1 Water Sample Analysis
get elements( relative error of result is less than 10%) Water sample of 5 mL( artificial seawater and the
are given in Table 2. East Lake water) , 1.0 mL of a 0. 1 moVL buffer solu-
Table 2 Tolerance l i t s of coexisting ions tion of NaOH-KH,PO, , and 0.5 mL of a 1.0% ( mass
Tolerance limit/ Tolerance limit/ fraction) dimethylglyoxime solution were added in a 10
Coexisting ion Coexisting ion
( pg mL-l) ( pg * mL 1 mL centrifugal flask. The pH value of the mixed solu-
K+ 2oooo Fez + 10
Cu2 10
tion was adjusted to 6.0 by dropwise addition of HC1 or
Na + 2oooo +
CaZ + 2500 Zn2 + 20 NaOH solution. After dilution, the resulting solution
MgZ + 2500 Mn2 + 10 was 10 mL, to which 2 mL of chloroform was added
Fe3 + 20 ~ 1 3 + 20 and the extraction was operated according to the proce-
6 Linearity, Relative Standard Deviation, and dure described previously. The contents of nickel and
Detection Limit palladium were extremely low in the water samples to
In the concentration scale of 5 to 100 ng/mL, the be determined. Therefore, spiked water samples were
proposed method shows good linearity for the determi- analyzed so as to evaluate the reliability of the method.
nation of nickel and palladium; the regression equa- The results of determination are given in Table 3 and
tions of the calibration curves are y = 0 . 2 1 -~ 0.22 and the recoveries of the concerned elements are 91% to
y = 0.2% + 1 . 2 5 [ y: signal intensity ( a. u. ) ; x : con- 102.8%.
centration of concerned element ( ng/mL) ] for nickel
Table 3 Analytical results for water samples
- mL-' ) (means
~ ~ ~~~
t-test was applied to evaluate the significance difference cance difference between the determined and the certi-
between the determined and the certified values. After fied values. This indicates that reliable results can be
the analysis, it was found that there was no signifi- obtained using the proposed method.
Table 4 Analytical results for certified reference material
Reference material Element - '
Certified d u e / ( pg g - ) - '
Measured/ ( p,g g - ) ( means i SD , n = 5 )
Stream sediment( GBWO7301a) Ni 56 *7 53.4 *3.5
Pd 5' 4.7i0.3
* Spiked value.
Conclusions Grotti M., Abelmoechi M. L., F . , et a l . , Anal. Bio-
anal. Chem., 2003, 375(2), 242
When compared to conventional ETV-ICP-OES
Kirkbright G. F. , Snook R. D . , Anal. C h . , 1979,
(without any chemical modifier), the usage of dime- 51(12), 1938
thylglyoxime as both extractant and chemical modifier Huang M., Jiang Z. C., Zeng Y. E . , J. Anal. Atom. Spec-
can enhance the sensitivity of determinations( calcula- trom. , 1991, 6 ( 3 ) , 221
Sun Y. C. , Hsieh C. H . , 1. Anal. Atom. Spectrom., 2002,
ted as the ratio of the slope of the calibration curves).
I 7 ( 2 ) , 94
The enhancement for nickel was 52.5 times and that Hu Bin, Jiang Zu-cheng, Zeng Yun-e, et 01. , Anal. Sci. ,
for palladium was 67.6 times. The enhancement of 1991, 7 ( 3 ) , 433
sensitivity may be caused by two factors. First, target Chen Shi-zhong, Peng Tian-you, Jiang Zu-cheng, et al. , J.
elements can be enriched through liquid-liquid extrac- Anal. Atom. Spctrom. , 1999, 14( 11 ) , 1723
Hang Yi-ping, Qin Yong-chao, Jiang Zu-cheng, et al. , Chem.
tion and the theoretical enrichment factor is 50. Se-
J. Chinese Universities, 2003, 24 ( 11 ) , 1980
cond, the usage of dimethylglyoxime as chelating agent Peng Tian-you , Jiang Zu-cheng , Chem. J. Chinese Univrrsitiu ,
increases the transport efficiency of nickel and palla- 1998, 1 9 ( 5 ) , 699
dium into ICP as gaseous form, improves the shape of Chen Shi-zhong, Peng Tian-you, Jiang Zu-cheng , Anal. k i t . ,
1999, 3 2 ( 2 ) , 411
the signal peaks, and enhances the sensitivity of the
Wu Ying-liang, Hu Bin, Jiang Zu-cheng, Chem. J. Chinue
analysis. Uniwrsitiu. , 2004,25( 1) , 50
Wu Ying-liang, Hu Bin, Peng Tian-you, et al. , Anal. Chim.
References Acta, 2001, 439, 153
Hill S. , Inductiwly Coupled Plmm Spectrometry and Its Applica- T a o S . , Kumamaru T . , J. Anal. Atom. Spectrom., 1996,
tiom, 1st Ed. , ShefXeld Academic Press Ltd. , Shaield , 1999, 1 1 ( 2 ) , 111
245 Fan Z. F. , Jiang 2. C. , Yang F. , et al. , Anal. Chim. Acta,
Balaram V. , Research J o u d of Chemistry and Environment, 2004,510(1),45
2002, 6 , 69 Xia Lin-bo, Hu Bin, Jiang Zu-cheng, et al. , Anal. Chem. ,
Nixon D. E. , Fasael V. A. , Kniaeley R. , Anal. Chem. , 2004, 76( l o ) , 2910
1974, 4 6 ( 2 ) , 210 Ueno K. , Imamura T. , Cheng K. L., Handbook of Organic
Maia S. M. , Pozebon D. , Curtius A. J. , J. A d . Atom. Spec- Analytical Reagentc, 2nd Ed. , CRC Press, Tokyo, 1992, 401
trom. , 2003, 1 8 ( 4 ) , 330 Honjo T. , Imura H. , Shima S. , et al. , Anal. Chem. , 1978,
Carey J. M., Caruso J. A. , Crit. Rev. Anal. Chem., 1992, 50(11), 1545
2 3 ( 5 ) , 397 Suzuki I. , Honjo T. , Terada K. , Bull. Chcm. Soc. Jq. ,
Resano M. , Garcia-Ruiz E. , Vanhaecke F. , et al. , J. Anal. 1990, 63(12), 3686
Atom. Spectrom. , 2004, 1 9 ( 8 ) , 958