Analyte Insensitive Electrode for pH Sensor Calibration

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Solution Overview

Problem

Conventional pH sensors face issues due to the instability of internal reference electrodes and the need for constant recalibration, as well as the fragility of glass membranes, which limits their use in high-temperature or pressure conditions, and the propensity for the electrolyte to clog due to salt precipitation.

Innovation Solution

The use of an analyte insensitive electrode (AIE) with an electrolytic layer, such as room temperature ionic liquids, to maintain a constant chemical environment for redox active materials, allowing for continuous internal self-calibration and reducing direct chemical interaction with the sample, thereby enhancing stability and accuracy.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If a conventional reference electrode with fixed ionic composition is used, then a stable constant potential is provided, but the electrolyte is isolated from the sample via a porous frit which propends to clog due to salt precipitation

Engineering Contradiction:
Improvestability of reference electrode potentialVSAvoidclogging of porous frit
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The patent extracts the redox couple from the fixed ionic composition electrolyte and places it directly in contact with the sample solution. This eliminates the need for a porous frit isolation barrier, preventing clogging while maintaining reference potential stability through the redox equilibrium.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent changes the parameter of ionic composition from fixed to variable by allowing the electrolyte to be in direct contact with the sample. The reference potential stability is maintained not by fixed composition but by the equilibrium of the redox couple, which compensates for ionic strength variations.

Inventive Principle:
Principle #35Parameter changes

2Ease of operation

If an internal reference electrode is used in a glass pH probe, then pH measurement is enabled, but the probe requires constant recalibration due to drift in reference electrode potential

Engineering Contradiction:
ImprovepH measurement capabilityVSAvoidstability of reference electrode potential
Core Design Contradiction:
Ease of operationVSReliability

Solution Approach 1:

The patent implements self-calibration by incorporating a redox couple that automatically adjusts to maintain equilibrium with the sample solution. The system serves itself by using the sample's own ionic composition to establish the reference potential, eliminating drift and the need for external recalibration.

Inventive Principle:
Principle #25Self-service

Solution Approach 2:

The redox couple provides continuous feedback to maintain equilibrium with the sample solution. The potential adjusts dynamically based on the sample's ionic composition, ensuring stable reference potential without drift or manual intervention.

Inventive Principle:
Principle #23Feedback

3Measurement precision

If a glass membrane is used in conventional pH probes, then pH sensitivity is achieved, but the fragile glass membrane renders probes unsuitable for high temperature or pressure conditions

Engineering Contradiction:
ImprovepH sensitivityVSAvoidmechanical strength of glass membrane
Core Design Contradiction:
Measurement precisionVSStrength

Solution Approach 1:

The patent replaces the mechanical glass membrane with a chemical sensing mechanism based on redox equilibrium. The sensing function is achieved through chemical interactions in solution rather than mechanical membrane properties, enabling operation under extreme temperature and pressure conditions.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The patent changes the sensing mechanism from mechanical (glass membrane potential) to chemical (redox equilibrium). This parameter change allows the sensor to operate in environments where glass membranes would fail, expanding the operational range to high temperature and pressure conditions.

Inventive Principle:
Principle #35Parameter changes

4Reliability

If the porous frit is kept wet to prevent clogging, then the reference electrode remains functional, but the electrode must be stored in KCl solution and requires constant maintenance

Engineering Contradiction:
Improvefunctionality of reference electrodeVSAvoidstorage and maintenance requirements
Core Design Contradiction:
ReliabilityVSEase of operation

Solution Approach 1:

The patent extracts the redox couple from the KCl electrolyte system and places it directly in the sample solution. This eliminates the need for separate storage in KCl solution and removes the requirement for keeping the frit wet, as no porous frit is used in the new design.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The redox couple system is self-sufficient and can be stored directly in the sample solution or in a compatible medium without special maintenance. The system automatically maintains its functionality through the equilibrium of the redox couple, eliminating the need for constant wetting or separate storage procedures.

Inventive Principle:
Principle #25Self-service

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The AIE provides a predictable, analyte-insensitive signal that can be used for internal calibration, improving the stability and longevity of pH sensors and expanding their applicability across varying conditions without the need for frequent recalibration.

Implementation Method 1

an electrolytic layer, which can be composed of, for instance and without limitation, room temperature ionic liquids (RTIL) or other ionic liquids or liquids with sufficient ionic strength

Methodology Applied
Scientific EffectIonic conduction: Conduction (electrical)

Implementation Method 2

the redox system and electrolyte are typically isolated from the sample under study via a porous frit or small aperture

Methodology Applied
Scientific EffectRedox reactions: Redox Reactions

Data Source

PatentEP2406620B1Device for providing a means for internal calibration in an electrochemical sensor
Publication Date: 2018.10.10 PARKER HANNIFIN CORP
  • EP2406620B1 patent drawingFigure 1
  • EP2406620B1 patent drawingFigure 2
  • EP2406620B1 patent drawingFigure 3

AI summary

Internally calibrated pH and other analyte sensors based on redox agents provide more accurate results when the redox active reference agent is in a constant chemical environment, yet separated from the solution being analyzed in such a way as to maintain electrical contact with the sample. Room temperature ionic liquids (RTIL) can be used to achieve these results when used as a salt bridge between the reference material and the sample being analyzed. The RTIL provides the constant chemical environment and ionic strength for the redox active material (RAM) and provides an electrolytic layer that limits or eliminates direct chemical interaction with the sample. A broad range of RAMs can be employed in a variety of configurations in such "Analyte Insensitive Electrode" devices.