EVALUATION OF A THEORY FOR THE SENSITIVITY AND SELECTIVITY OF A POLYMER DIFFUSION PLASTICIZATION BASED SOLID-STATE ELECTROCHEMICAL GAS-CHROMATOGRAPHY DETECTOR

被引:21
作者
BARBOUR, CJ [1 ]
MURRAY, RW [1 ]
PARCHER, JF [1 ]
机构
[1] UNIV MISSISSIPPI,DEPT CHEM,UNIVERSITY,MS 38677
关键词
D O I
10.1021/ac00006a010
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
A theory for the sensitivity and selectivity of a diffusion-plasticization based electrochemical gas-liquid chromatography (ECGC) detector is developed and evaluated. The detector is based on the microelectrode voltammetry of an electroactive solute dissolved in a thin film of polymer electrolyte exposed to the column effluent gas. At constant temperature, the integrated detector peak response (i.e., charge) is proportional to the partition coefficient K(part) of the analyte into the detector polymer phase and to a dynamics parameter beta describing the extent to which the diffusion coefficient of the electroactive solute in the polymer phase is enhanced by the partitioned organic analyte. The dependency of beta on the particular kind of functional group of the analyte molecule suggests a mechanism for diffusion-plasticization based on specific interactions with the polymer and with the electrolyte dissolved in the polymer. The dependency of the ECGC detector response on temperature is complex, being affected by changes in polymer-phase crystallinity.
引用
收藏
页码:604 / 610
页数:7
相关论文
共 28 条
[1]  
ABRANTES TMA, 1988, SOLID STATE IONICS, V18, P315
[2]   ELECTROCATALYSIS OF DIOXYGEN REDUCTION IN AQUEOUS ACID AND BASE BY MULTIMOLECULAR LAYER FILMS OF ELECTROPOLYMERIZED COBALT TETRA(ORTHO-AMINOPHENYL)PORPHYRIN [J].
BETTELHEIM, A ;
WHITE, BA ;
MURRAY, RW .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1987, 217 (02) :271-286
[3]   APPLICATION OF A POLYMER SOLID ELECTROLYTE FOR THE VAPOR-PHASE ELECTROCATALYSIS OF DIOXYGEN REDUCTION BY SOME COBALT PORPHYRINS [J].
BETTELHEIM, A ;
REED, R ;
HENDRICKS, NH ;
COLLMAN, JP ;
MURRAY, RW .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1987, 238 (1-2) :259-276
[4]  
BOCKRIS JO, 1969, FUEL CELLS THEIR ELE, pCH2
[5]   THE USE OF NARROW GAP MICROELECTRODES AS SENSITIVE AND SPECIES SELECTIVE GAS-CHROMATOGRAPHIC DETECTORS [J].
BRINA, R ;
PONS, S .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1989, 264 (1-2) :121-130
[6]   MOLECULAR TRANSPORT IN LIQUIDS AND GLASSES [J].
COHEN, MH ;
TURNBULL, D .
JOURNAL OF CHEMICAL PHYSICS, 1959, 31 (05) :1164-1169
[7]  
DEXI W, 1989, CHEM MATER, V1, P357
[8]   PULSE VOLTAMMETRY WITH MICROVOLTAMMETRIC ELECTRODES [J].
EWING, AG ;
DAYTON, MA ;
WIGHTMAN, RM .
ANALYTICAL CHEMISTRY, 1981, 53 (12) :1842-1847
[9]   STATISTICAL MECHANICS OF SWELLING OF NETWORK STRUCTURES [J].
FLORY, PJ .
JOURNAL OF CHEMICAL PHYSICS, 1950, 18 (01) :108-111
[10]   Solid-State Voltammetric Measurement of Plasticization Transport Enhancement in Ionically Conducting Poly(ethylene oxide) Films [J].
Geng, L. ;
Longmire, M. L. ;
Reed, R. A. ;
Parcher, J. F. ;
Barbour, C. J. ;
Murray, Royce W. .
CHEMISTRY OF MATERIALS, 1989, 1 (01) :58-63