Chemical Sensing Employing pH Sensitive Emeraldine Base Thin Film for Carbon Dioxide Detection

Abstract

Respiration, or CO2 evolution, is a universal indicator for all the biological activities. Among many potential applications, the measurement of CO2 evolution has been found to be a rapid and nondestructive means for examining microbial contamination of food. The sensor developed in this work consists of a thin emeraldine base-polyaniline (EB-PAni) film. In the first half of the project the effect of carbon dioxide over the conductivity of a composite film of emeraldine base polyaniline and poly(vinyl alcohol) in N-methyl pyrrolidone (NMP) respectively was tested. Argon gas or mixture of argon and 5% CO2 were circulated through the glass cell containing the polymer film deposited on interdigitated electrode and exposed to specific humidity levels fixed by aqueous supersaturated salt solutions. In the second half of the project a thin emeraldine base film in NMP was directly deposited on interdigitated electrode and the respective sensor inserted in water. Carbonic acid solutions of various pHs were generated by bubbling specific mixtures of carbon dioxide and argon. Conductivity measurements were performed by impedance spectroscopy throughout the project. The sensing mechanism is based on intermediate stages of the transformation of the emeraldine base polyaniline to a conductive salt type (ES-PAni). This EB-ES transformation is the consequence of the exposure of EB-PAni to a protonic acid and is accompanied by a change in the conductivity of the polymer film. Carbonic acid, unfortunately, is a very weak acid and is unable to induce a conductivity change, but the intermediate steps that predetermine this transformation are detected by impedance spectroscopy even when the overall conductivity of the film is unchanged. The composite thin film developed in the first part of the project showed poor sensing characteristics: limited dynamic range, drift, instability and slow time response. However, the sensor design employed in the second half of this work, coupled with impedance spectroscopy measurements, revealed valuable information about conduction mechanisms at pH levels were the overall conductivity of the film remained unchanged. Typical impedance spectra for the emeraldine thin films for a frequency sweep between 3.2 E7 to 1 Hz shows a single semicircle. The overall conductivity of the film (5?10-4 S/cm) does not change when CO2 is bubbled through the water in which the sensor is immersed, but an additional semicircle starts to appear at low (less than 200 Hz) frequency corresponding to lowering the pH of the solution below 5.0. The original semicircle diminishes in size but maintains its initial peak frequency. The EB film is very sensitive to pH changes, therefore an additional semicircle appears in unpurified argon gas due to the reduction of the pH of water solution to 4.65. The same mechanism is displayed in hydrochloric acid solutions of various pH. The formation of the second semicircle depends on the initial conductivity of the emeraldine base film, a film displaying an initial conductivity of 4.8 ? 10-3 S/cm forming the second semicircle at a pH of 5.85. The appearance of the second semicircle is most likely due to a preferential protonation in the insulating matrix of the polymer film. The overall conductivity of the film increases when the level of protonation in the insulating portion of the film reached a level close to the protonation level in the scattered metallic islands, allowing the electron-hopping mechanism to became active. The sensor output is stable and reproducible even after 11 months from the polymer film deposition.