Name: dynamic electrochemical measurement of chloride ions
Uploaded: 2016-02-05T13:00:00
Description: Watch this Scientific Journal Video about Dynamic Electrochemical Measurement of Chloride Ions at JoVE.com

This work is a part of the STW project "Integral solution for sustainable construction (IS2C, Fleur van Rossem for her support during the chip fabrication, Justyna Wiedemair for the chip design and Allison Bidulock for her support during the manuscript preparation.

1. Chip Fabrication
Note: The chip consists of an Ag/AgCl working electrode (WE), an Ag/AgCl pseudo-reference electrode (pseudo-RE) and a platinum counter electrode on a glass chip. The silver metal is deposited on a glass chip, using standard cleanroom processes16. It is then chloridized in 0.1 M FeCl3 solution for 30 sec to form an AgCl layer over the surface. The Ag/AgCl WE (area = 9.812 mm2) is located in the center, surrounded by the Ag/AgCl pseudo-RE as sho...

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The transition time is the moment of inflection; it is theoretically independent of the reference potential i.e., the reference electrode. Therefore any metal wire can be used as a pseudo-reference electrode for transition time measurements. In contrast to the existing potentiometric measurement of chloride ions in concrete this method enables a long-term and calibration free measurement. Furthermore the sensitivity and the detection range of concentration can be tuned by adjusting the applied current pulse. For...

A chloride ion sensor based on the transition time measurement of an Ag/AgCl electrode is presented. The aim is to avoid the inherent drifts during the long-term continuous monitoring of the chloride ions in the electrolyte. Chronopotentiometric measurement, which is a dynamic measurement approach, of an Ag/AgCl electrode is used for this purpose. Here a rate of change of potential of an Ag/AgCl electrode is measured during a stimulus (galvanostatic pulse). The advantage of this approach is demonstrated by eluding the liquid-junction reference electrode and instead using any metal wire as a pseudo-reference electrode, therefore allowing the detection of Cl&#713; ions concentration for long-term (years) and in situ applications, such as measurement inside concrete structures.
Chloride ions in concrete structures is one of the major causes of degradation1,2. It initiates pitting corrosion in the reinforcement steel and results in the ultimate failure of the structure3. Therefore, measuring Cl&#713; ions in concrete is inevitable to predict the service life and maintenance cycle of a structure4,5. Different sensing principles have been reported for chloride ion measurement in concrete such as electrochemical6,7, optical8,9 and electromagnetic10,11. However, optical and electromagnetic methods have bulky setups, are difficult to integrate as a stand-alone system and have issues with selectivity12. In electrochemical technique, potentiometric measurement of an Ag/AgCl electrode is the state of the art approach6,7,13. Despite promising results, this approach is limited to lab-scale measurement since the drifts in reference potential and diffusion potential drop results in flawed data14,15. A transition time approach based on the dynamic electrochemical measurement (DEM) could alleviate the problem due to potential drift16.
In the DEM, a system&#39;s response to an applied stimulus is measured17-19. The example of such a system is chronopotentiometry. Here an applied current pulse is used as a stimulus depleting ions near the electrode surface and the corresponding potential response is measured. An anodic current at an Ag/AgCl electrode initiates a faradaic reaction (Ag + Cl&#713; <img alt="Figure 1" src="/files/ftp_upload/53312/arrow.jpg" />AgCl + e&#713;) resulting in a depletion of Cl&#713; ions near electrode surface. The potential change is a function of the applied current and the concentration of the (selective) ions in the electrolyte12,20. The moment these ions deplete completely near the electrode surface the rate of change of potential rises rapidly, giving an inflection point21. The inflection point on the potential-time response curve (chronopotentiogram) shows the transition time and can be determined from the maximum of the first derivative of the potential response22. The transition time is a characteristic of the ion concentration. This approach has been used to determine different ions concentration17 and the pH of electrolytes23,24. In case of an Ag/AgCl electrode as a working electrode (to which current is applied) the depleting ions will be chloride ions17. Therefore measuring its transition time will determine its concentration.

<table border="0" cellpadding="0" cellspacing="0" width="1009">
	<tbody>
		<tr height="25">
			<td height="25" style="height:25px;width:373px;">Platinum wire (&#8805;99.99% trace metals)</td>
			<td style="width:292px;">Sigma Aldrich, the Netherlands</td>
			<td style="width:172px;">EP1330-1EA</td>
			<td style="width:172px;"></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Potassium chloride (BioXtra, &#8805;99.0%)</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td>P9333-500G</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Potassium hydroxide (90% pure reagent grade)</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td>484016-1KG</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Ferric chloride&#160;</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td>451649-1G</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">potassium nitrate (&#62; 99% reagent grade)&#160;</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td>P6083-500G</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Ag/AgCl liquid junction reference electrode&#160;</td>
			<td>BASi, USA</td>
			<td>model MF-2079</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">VSP potentiostat</td>
			<td>Biologic Science Instruments, France</td>
			<td>VSP 300</td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Steel wire</td>
			<td>Microlab TU Delft</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;">Silver wire&#160;</td>
			<td>Sigma Aldrich, the Netherlands</td>
			<td></td>
			<td></td>
		</tr>
	</tbody>
</table>

dynamic electrochemical measurement of chloride ions

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver chloride electrode is used extensively for potentiometric measurement of chloride ions concentration in electrolyte. In this measurement, long-term and continuous monitoring is limited due to the inherent drift and the requirement of a stable reference electrode. We utilized the chronopotentiometric approach to minimize drift and avoid the use of a conventional reference electrode. A galvanostatic pulse is applied to an Ag/AgCl electrode which initiates a faradic reaction depleting the Cl&#713; ions near the electrode surface. The transition time, which is the time to completely deplete the ions near the electrode surface, is a function of the ion concentration, given by the Nernst equation. The square root of the transition time is in linear relation to the chloride ion concentration. Drift of the response over two weeks is negligible (59 &#181;M/day) when measuring 1 mM [Cl&#713;]using a current pulse of 10 Am-2. This is a dynamic measurement where the moment of transition time determines the response and thus is independent of the absolute potential. Any metal wire can be used as a pseudo-reference electrode, making this approach feasible for long-term measurement inside concrete structures.

The Ag/AgCl electrode is fabricated on a glass chip (Figure1) using a standard cleanroom process. The chronopotentiometric measurement setup (Figure 2) was used and response was measured using a potentiostat. To observe the effect of Cl&#713; ion concentration on the transition time, solutions containing 4, 5 and 6 mM of Cl&#713; ions in a 0.5 M KNO3 background are measured (Figure 3). The calibration curve of the square root o...

Watch this Scientific Journal Video about Dynamic Electrochemical Measurement of Chloride Ions at JoVE.com

Dynamic Electrochemical Measurement of Chloride Ions

Dynamic measurement of chloride ions is presented. Transition time of an Ag/AgCl electrode, during a chronopotentiometric technique, can give the concentration of chloride ions in electrolyte. This method does not require a stable conventional reference electrode.

This protocol describes the dynamic measurement of chloride ions using the transition time of a silver silver chloride (Ag/AgCl) electrode. Silver silver ...

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