Using matrix effects as a probe for the study of the charge-transfer mechanism in inductively coupled plasma-atomic emission spectrometry

被引:44
作者
Chan, GCY [1 ]
Hieftje, GM [1 ]
机构
[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
关键词
inductively coupled plasma-atomic emission spectrometry; excitation mechanisms; charge transfer; matrix effects; transition metals;
D O I
10.1016/j.sab.2003.10.004
中图分类号
O433 [光谱学];
学科分类号
0703 ; 070302 ;
摘要
A novel method is presented for using matrix effects as a probe for the charge-transfer reaction between analyte atoms and argon ions in inductively coupled plasma-atomic emission spectrometry (ICP-AES). The method is based on the fact that the matrix effect caused by Ca or Ba depends on whether the studied analyte spectral line is from an ion or a neutral atom. Because the charge transfer reaction directly links atomic and high-energy ionic levels of the analyte, ionic spectral lines excited by charge transfer behave more like neutral-atom emission. As a result, quasi-resonant ionic emission lines exhibit a unique matrix effect character and can be easily identified. A commercial simultaneous full UV-Vis wavelength-coverage ICP spectrometer was used to study the responses of a large pool of spectral lines from a total of 22 elements in the presence of Na, Ca and Ba matrices. Candidate elements with charge-transfer character were thereby identified. The results match closely with those reported in the literature. The technique was further used to study charge-transfer reactions exhibited by the fourth-row metals from Sr to Sb. With the exception of Cd, Sr and Mo, all the other studied fourth-row metals showed positive evidence of excitation and ionization by charge-transfer from argon ion. While Sr showed negative results, the charge transfer-character of Cd and Mo could not be confirmed. It was also found that charge transfer can originate from other low-lying atomic analyte levels, in addition to the atomic ground state, and that charge-transfer reactions can occur at an appreciable rate even with a negative energy defect (i.e. negative DeltaE) up to -1.6 eV. (C) 2003 Elsevier B.V. All rights reserved.
引用
收藏
页码:163 / 183
页数:21
相关论文
共 43 条
[31]   CORRELATION SPECTROSCOPY AS A PROBE OF EXCITATION AND IONIZATION MECHANISMS IN THE INDUCTIVELY COUPLED PLASMA [J].
OGILVIE, CM ;
FARNSWORTH, PB .
SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY, 1992, 47 (12) :1389-1401
[32]   INDUCTIVELY-COUPLED PLASMA OPTICAL-EMISSION SPECTROMETRY USING NEBULIZERS WITH WIDELY DIFFERENT SAMPLE CONSUMPTION RATES [J].
OLESLK, JW ;
KINZER, JA ;
HARKLEROAD, B .
ANALYTICAL CHEMISTRY, 1994, 66 (13) :2022-2030
[33]  
Radzig A. A., 1985, Reference Data on Atoms, Molecules and Ions
[34]   The effect of sodium on analyte ionic line intensities in inductively coupled plasma atomic emission spectrometry: Influence of the operating conditions [J].
Romero, X ;
Poussel, E ;
Mermet, JM .
SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY, 1997, 52 (04) :495-502
[35]  
SMITH PL, 2002, ATOMIC SPECTRAL LINE
[36]   CHARGE-TRANSFER EXCITATION PROCESSES IN THE GRIMM LAMP [J].
STEERS, EBM ;
FIELDING, RJ .
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, 1987, 2 (02) :239-244
[37]   OBSERVATIONS ON THE USE OF THE MICROWAVE-BOOSTED GLOW-DISCHARGE LAMP AND THE RELEVANT EXCITATION PROCESSES [J].
STEERS, EBM ;
LEIS, F .
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, 1989, 4 (02) :199-204
[38]   Matrix-induced shift effects in axially viewed inductively coupled plasma atomic emission spectrometry [J].
Stepan, M ;
Musil, P ;
Poussel, E ;
Mermet, JM .
SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY, 2001, 56 (04) :443-453
[39]  
THOMASSEN AJW, 1992, TUTORIALS MOTOR BEHA, V2, P249
[40]   Elemental matrix effects in ICP-AES [J].
Todolí, JL ;
Gras, L ;
Hernandis, V ;
Mora, J .
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY, 2002, 17 (02) :142-169