IES59700B2 - Reference electrodes - Google Patents

Description

TITLE OF THE INVENTION Reference Electrodes BACKGROUND OF THE INVENTION a) Field of the Invention This invention relates to reference electrodes.

Conventional reference electrodes are generally one of two types ·· Ag/AgCl electrodes and calomel electrodes. Reference electrodes are used together with measuring electrodes in electrochemical systems to determine the concentration of ions in a sample i..e. the pH or pX where X represents an ion. The electrical potential of the reference electrode should remain as constant as possible throughout the measuring process while the potential of the measuring electrode,, which can be ion selective, is proportional to the concentration of the ion being tested in the sample. The potential of the reference electrode is kept substantially constant due to the presence of a saturated electrolyte salt bridge within the cell. The potential difference between the reference electrode and the measuring electrode is indicative of the concentration of the ion and is displayed on a millivolt instrument such as a potentiometer.

The electrolyte generally leaks very slowly through an opening in the reference electrode, for example at a porous plug, to form a liquid junction between the salt bridge and the sample solution being tested. - 2 The potential of the complete electrochemical cell made up of the measuring electrode and the reference electrode can be represented by the following equation ^Cell ~ ^meas ' ^ref + ^j where Emeas is the potential of the measuring electrode, is the potential of the reference electrode and Ej is a junction potential.

The junction potential arises from the different rates of mobility of anions and cations at the interface between two electrolytic solutions. Ideally, the junction potential of the reference electrode should have a negligible variation between solutions as otherwise the change in the junction potential will appear as an error in the overall potential calculated for the sample and hence the concentration determined.

In certain applications, a precipitate can form at the junction of the reference electrode and the sample solution where the electrolyte of the reference electrode -flows into the sample. These precipitates can clog the opening «and therefore interfere with the liquid junction potential and give rise to measuring errors. b) Description of the Related Art European Patent Publication 0 247 535 Al Russell et. al. describes wet and dry forms of reference electrode. In the “wet” form, a glass tube housing a silver wire and electrolyte and sealed with a porous plug is covered by a sheathing made of a polymer which is mixed with crystalline potassium chloride or another electroconductive additive before curing or polymerisation. In the dry form as described with reference to Figure 4 or 6, a chloridised silver wire has a sheathing made of a polymer mixed with a conductive additive, while as defined in Claim 5 the sheathing is made of a polymer which is mixed before curing or polymerisation with crystalline potassium chloride or another electroconductive additive, to which finely dispersed silver chloride is added. Other electroconductive additives - 3 mentioned include lithium chloride, potassium nitrate, or sodium nitrate. The polymers identified for the sheathing are polyvinyl f ester, polyethylene, polypropylene, polyvinyl chloride, or epoxy resin.

European Patent Publication No. 0 100 988 Al Shimomura et. al. describes a reference electrode prepared by coating the surface of a conductive substrate with a silver complex polymer compound which is either a compound prepared by complex formation between a polymer compound containing a co-ordinating nitrogen atom and a silver ion, or such a complex compound containing a silver halide.

United States Patent Specification No. 4913793 Leonard describes a reference electrode, optionally in combination with a measuring electrode in which the salt bridge comprises anionic and cationic ion exchange polymer.

U.S. Patent Specification No. 4,,112,352 describes a combined reference and measuring electrode fitted with a thermocompensator. However, wooden plugs must be used in order to erasure electrical communication between the reference electrode and sample solution. However, the wooden plug comprises a liquid junction which can result in contamination of the sample and failure of the electrode through leakage.

SUMMARY OF THE INVENTION It is an object of the present invention to provide novel forms of reference electrode in which a polymer with an electrically conductive additive is used to isolate a reference electrode electrolyte from the sample solution while allowing electrical contact between the two.

The present invention provides a reference electrode for use with a measuring electrode for measuring ion activity in a sample solution, said reference electrode comprising: an electrode chamber for holding electrolyte in complete isolation from the sample solution, - 4 and an electrode element in said electrode chamber, wherein at least a portion of one of the walls which define said chamber is formed of wall material comprising an immobilised non-porous polymer having one or more salts of potassium, sodium and/or lithium mixed through at least one region of said wall material before curing of the polymer to render said region of the wall material electrically conductive, said wall providing a physical barrier between the electrolyte and the sample solution but permitting electrical communication between them.

The salt(s) in the wall material form part of the salt bridge of the reference electrode. No glass tube is required to hold the electrolyte. It is not necessary for the wall material to contain dispersed silver chloride.

Although the present invention is not limited by any theory, it is believed that the salt(s) render the wall material electrochemical 1y-ionically conductive. The amount of the salt(s) must be an amount effective to render the wall material electrically conductive, more particularly electrochemically-ionically conductive, in the region through which electrical communication is required.

In a preferred embodiment the polymeric wall material is in tubular form. According to one feature of the invention, the wall material is in the form of a tube closed at one end.

The electrode element may be of metal wire, gauze mesh or leaf, especially of silver, more particularly chloridised silver wire or may be a metal structure which optionally may define at least part of one of the walls of the chamber, e.g. a metal cylinder, especially of silver or coated therewith, more particularly chloridised silver.

In an embodiment for use in monitoring solutions passing through pipes etc. a flowthrough reference electrode is provided comprising a tube of the conductive wall material whose internal surface defines a passage through which the sample solution can flow, and a housing radially outward of said tube, the tube and housing defining an - 5 annular chamber to hold electrolyte, and an electrode element housed in said chamber.

In another embodiment for use in monitoring flowing solutions, the wall material may be in the form of a body defining a passage through which the solution can flow and also at least partly defining the electrode chamber such that electrolyte in the electrode chamber is in electrical communication with flowing solution.

In yet another embodiment the electrode assembly further comprises a thermocompensator.

A further embodiment combines a reference electrode of the present invention with a measuring electrode to form a single-unit electrode assembly. This electrode assembly may comprise a conventional measuring electrode fitted inside a tube of the conductive wall material so as to define an annular chamber between them to hold electrolyte, with the measuring electrode as the inner wall and the tube of conductive material as the outer wall, and an electrode element housed in said chamber.

The electroconductive wall material preferably comprises a polymeric support containing dispersed salts selected from chloride, nitrate and sulphate salts of potassium, sodium and/or lithium. A major proportion of a potassium salt with a minor proportion of a lithium salt is preferred (e.g. in a ratio from 8.5:1 to 9.5:1), the presence of lithium being advantageous to reduce the resistance and thus to reduce response time for the electrode. The polymers useful in the wall material of the present invention should themselves have good electrical insulation properties, e.g. vinyl ester resins, polyesters, polyethylene, polypropylene, polyvinyl chloride or epoxy resins. The vinyl ester resins are preferred because of their chemical resistance. The polymers are cured under conventional conditions for the respective polymers to form a solid, immobilised non-porous body containing the salt(s) dispersed therethrough. Typical curing conditions are from 10 to 60 minutes at a temperature of between 40 and 10°C. Epoxy resins curable bv ultra violet light may also be suitable.

Some washing out or leaching of the salts from the exposed - 6 surface of the electroconductive wall material into the sample solution may occur during use. However, if the concentration of salt within the wall is high, this loss does not significantly affect the performance of the electrode. Leaching of the salts is a surface phenomenon and no penetration of the sample solution into the reference electrolyte is observed. Since some wash out is observed, the salt(s) in the wall material must be chosen carefully. It must not react with any species in the sample solution (which may form insoluble salts) and it must not interfere with the signal from the measuring electrode.

Typically the wall material comprises from 35-55% by weight of salt(s) dispersed in from 5737% by weight of polymer resin so that the salt(s) is/are densely dispersed throughout the material (the percentages being based on the total weight of the composition). The preferred resin/KCl ratio is about 48/44 by weight as this produces a good curing mix and a high KC1 concentration. Additives such as initiators and accelerators used in promoting the curing process may be present in small amounts. In cases where the wall material acts as a protective cover surrounding a silver halide containing cell (e.g. an Ag/AgCl electrode) it is advantageous that the protective cover be opaque so as to prevent photodegradation. To achieve this, graphite or other colourants may be dispersed in suitable amounts in the composition.

The electrode of the present invention overcomes the problems of conventional reference electrodes by isolating the electrolyte from the sample solution. It is also advantageous over other electrodes in that it is simple to construct. The wall material in tubular form may be manufactured by moulding or spinning techniques, preferably by spinning during curing, more particularly by spinning about a horizontal axis. Alternatively the wall material may be moulded and then left standing vertically during curing, so that the salt concentration tends to increase in the lower region. If the salt is of relatively high molecular weight (e.g. KNO^), a high proportion of the salt may settle in the lower region until that lower region is saturated (or loaded to full capacity) with the salt. In such a case, the weight percentage of salt(s) in the total polymer resin may be less than the percentage ranges indicated above, e.g. 15 ~ 35%.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following example illustrates how the electroconductive wall material may be produced: Example 1 Potassium chloride is dried for 1 hour at 150°C and then placed in a mill and ground to a fine powder. Lithium chloride is treated in a similar manner. The powdered salts (potassium chloride 90 g, lithium chloride 10 g) are added along with optionally 2 g of Black Graphite powder to a vinyl ester resin (100 g) and mixed thoroughly at 25°C. A filler such as quartz may also be added for mechanical strength, typically in the amount of 5 gm although this can be varied.

Prior to curing the following are added to the mixture (percentages are by weight of total composition): 1.5 - 2.0 % Methyl ethyl ketone peroxide (initiator) 0.2 - 3.0 % Cobalt octoate (accelerator) 0.5 - 2.0 % Dimethyl! ani lit we (accelerator) 1.0 - 2.0 % BYK-A515 (air release agent) * BYK is a registered trademark of BYK-Chemie GmbH.

One particular example of the total composition is as follows (percentages by weight): Vinyl ester resin48 KC144 LiCl5 Graphite1 Methyl ethyl ketone peroxide1 Cobalt Octoate0.5 Dimethylaniline0.5 BYK A-5150.5 The mixture is then cast in a cylindrical glass form and heated - 8 to 40°C for 10 minutes. Alternative!y, the mixture can be allowed to cure at a warm ambient temperature overnight. The glass form is allowed to stand vertically during curing. A tube closed at the bottom may be formed in this way. Alternatively, a cylindrical block having a concave base or recess can be formed using a suitable mould made up of a cylindrical form with a removable neoprene bung in its base. To release the hardened mixture from the form, the form is placed in an autoclave and heated to about 120°C for 10 minutes. This causes the cured part to shrink allowing it to be removed from the form. The tube of the cured immobilised composition is rigid and self-supporting. It is not porous to electrolytic solutions. If desired, the internal and/or external surface of the tube may be abraded lightly to remove a surface film of polymer and expose the salt content.

Example 2 In an alternative embodiment of a reference electrode, particularly for analysing a solution containing nitrate ions (such as an aqueous mixture of silver nitrate and a halide salt), one particular example of the total composition for the wall material is as follows (percentages by weight): Vinyl ester resin100 KNO320 Methyl ethyl ketone peroxide2 Cobalt Octoate2 BYK A-5151 The mixture is then cast in a cylindrical glass mould and heated to 40°C for 10 minutes. The glass mould is allowed to stand vertically during curing, so that the KNO^ settles to the lower region of the mixture. A tube closed at the bottom may be formed in this way, with a high concentration of KNO^ in or adjacent to the bottom of the tube. - 9 Example 3 In an alternative embodiment, the composition of Example 1 can be prepared with the addition of glass fibre in the amount of approximately 0.35 gm. Preferably, glass fibre having a 6 mm length is used. The glass fibre is inactive electrically but provides reinforcement. The mixture is then cast in a cylindrical glass mould and several moulds are inserted in pods which are spun horizontally at between 1000-2000 rpm, preferably 1000 rpm, for 30 minutes and at a temperature of up to 80°C. Once cooled the wall material can be removed from the moulds.

In an alternative embodiment, a tube of wall material can be formed having active and inactive regions i.e. the wall can be made up 15 of an electroconductive region of active material containing salt(s) in accordance with the invention and an electrically nonconductive region of inactive material. Electrically nonconductive wall material is made up of a composition as described in Example 1 but with the omission of the K and Li' salts- A horizontal spinning process described above may be used. However, in this process, the glass mould is first smeared on its internal surface with inactive material in order to ensure an even bonding between the active and inactive components. Typically. 0.75 gm of active material is used and 5.5 gm of inactive material. The 0.75 gm batch of active material is injected into the mould at one end and a 5.5 gm batch of the inactive material is injected into the mould at the other end so that the two batches of material meet inside the mould. The mould is inserted into the horizontal spinning pod as previously described and the spinning process repeated such that a tubular wall is obtained having active and inactive regions.

The electroconductive wall material prepared in the Examples as described above is intended for use following sterilization in the embodiments of the invention as described below. - 10 BRIEF DESCRIPTION OF THE DRAWINGS Several embodiments of the invention are illustrated in the accompanying drawings, in which: Figure 1 is a diagrammatic longitudinal cross section of one embodiment of a reference electrode: Figure 2 is a diagrammatic longitudinal cross section of a second embodiment; Figure 3 is a diagrammatic longitudinal cross section of an embodiment of a combined reference electrode/measuring electrode assembly; Figure 4 is a diagraranatic longitudinal cross section of an embodiment of a flow through reference electrode; Figure 5 is a diagram of a two-rod electrode assembly for pH measurements using the reference electrode of Figure 1; Figure 6 is a diagrammatic longitudinal cross-section of an alternative embodiment of a combined reference electrode/measuring electrode assembly; Figure 7 is a diagrammatic longitudinal cross-section of a combined reference electrode/measuring electrode assembly also combined with a thermocornpensator; Figure 8 is a diagrammatic longitudinal partial cross-section of an alternative embodiment of a combined reference electrode/measuring electrode assembly also combined with a thermocompensator; Figure 9 is a diagrammatic longitudinal partial cross-section of the electrode assembly of Figure 7 in a casing with the measuring electrode recessed; Figure 10 is a diagrammatic longitudinal partial cross-section - 11 of an alternative embodiment of a combined reference electrode/ measuring electrode assembly combined with a thermocompensator in a casing with the measuring electrode protruding; Figure 11 is a diagrammatic longitudinal partial cross-section of yet an alternative embodiment of a combined reference electrode/measuring electrode assembly combined with a thermocompensator in a casing with the measuring electrode positioned in a notch; Figure 12 is a diagrammatic longitudinal partial cross-section of a block reference assembly comprising the reference electrode of Figure 1, and Figure 13 is a longitudinal partial cross-section side view of a reference electrode of the invention in the form of a HPLC flowthrough cell.

As shown in Figures 1 and 5, a reference electrode comprises a tx?be 1 of the electroconductive wall material (as described above) closed at one end and defining a salt bridge chamber 2 for holding electrolyte and an electrode element 3 housed in the chamber 2 and isranersed in the electrolyte. The electrode element is suitably a galvanically chloridised silver wire., while the electrolyte is suitably a KC1 solution (eg. at about 2.7 M), or a gel of hydroxyethvl-cellulose mixed with KC1. Because silver chloride is highly soluble in a concentrated solution of potassium chloride, the electrolyte solution should be saturated with silver chloride to avoid removal of silver chloride from the electrode wire. At the top of the tube 1, the electrode wire is joined to a platinum plug which seals a small glass tube 4. 0-ring seals 6 are provided around the glass tube 4 to seal the electrolyte in the chamber 2.. A further length of silver wire 5 connects the electrode to a coaxial cable which leads to a measuring instrument 40. When the tube 1 is placed in a sample solution 41 (as shown in Figure 5), the electrolyte in the chamber 2 is completely isolated from the sample solution but is in electrical communication therewith because of the salt in the wall material of the tube 1. No glass tube or porous plug as described in EP 0 247 535 is present.

This reference electrode may be used in a two-rod electrode assembly with a measuring electrode 10 for pH measurements as shown in Figure 5.

As shown in Figure 2, a second embodiment is similar to that of Figure 1 but it utilises a tube la of glass which is open at both ends. A plug 7 of cotton wool wadding is provided at the lower end of the tube la. The tube la defines most of the chamber 2 containing electrolyte and housing the electrode wire 3 as in the embodiment of Figure 1. The tube la is covered in a sheath 8 of the electroconductive wall material which, in particular, extends around the lower end of the tube la to provide a wall which seals the lower end of the tube and isolates electrolyte in the chamber 2 from a sample solution into which the reference electrode is immersed. The sheath 8 has been left standing vertically during curing so that the salt has fallen to the lower part of the sheath, surrounding the outlet of the tube la, which is the ooly region of the sheath where a high concentration of salt is required. The «upper part of the sheath 8 is itself encased in a sleeve 9 of inert plastics material (e.g. epoxy resin) or glass which is not electrically conductive. This eliminates a possible error arising from the extent of immersion of the reference electrode in the sample solution.

The embodiment of Figure 3 is a combined (or single rod) assembly which has a measuring electrode 10 extending axially through the middle. The measuring electrode comprises a tube 11 of non-ion responsive glass of high resistance and a bulb 12 of pH or pX responsive glass which closes the lower end of the tube 11. A conventional Ag/AgCl electrode wire 13 is housed inside the tube 11 and bulb 12, immersed in a conventional pH buffer filling solution 37. Radially outwardly of the reference electrode there is an annular chamber 22 which houses the reference electrode wire 23 (e.g. an Ag/AgCl electrode) immersed in the electrolyte e.g. a KC1 electrolyte as described with respect to Figure 1, saturated with AgCl. The inner perimeter of the chamber 22 is defined by the tube 11 of the measuring electrode, while the outer perimeter of the chamber 22 is defined by a - 13 tube 21 of the electroconductive wall material. Double O-ring seals 24, 25 are provided at the top and bottom of the chamber, sealing against the tubes 11 and 21 respectively. Electrode wires 13 and 23 are connected from the top of the assembly through a millivolt measuring instrument.

When the electrode assembly of Figure 3 is immersed in a sample solution, the electrolyte in chamber 22 is completely isolated from the sample solution by the tube 21 and the 0-ring seals 25, but is in 10 electrical communication therewith because of the salt in the wall material of the tube 21.

Figure 4 shows an embodiment of the invention in the form of a “flowthrough reference electrode. A tube 31 of the conductive wall 15 material forms a conduit for the sample solution to be analysed.

Radially outward of the tube 31 there is a chamber 32 which is generally annular but which has a radially extending arm 34 through which the reference electrode wire 33 (e.g. Ag/AgCl electrode) projects into the annular region of the chamber 32, in which the wire 20 is wrapped helically around the tube 31.. The inner perimeter of the chamber 32 is defined by the tube 31, while the outer perimeter of the chamber is defined by a housing 35 which may suitably be of glass or plastics material. 0-rings 35 are provided between the tube 31 and the housing 35 to seal electrolyte (e.g.

Figure 6 shows an alternative embodiment of a combined (or single rod) assembly which has the measuring electrode 10 again extending longitudinally through the middle. The measuring electrode 35 10 is broadly similar to the one previously described in that it is made up of a tube 11 of non-ion responsive glass and a bulb 12 of pH or pX responsive glass. A conventional Ag/AgCl electrode wire 13 is housed inside the tube 11 and bulb 12 and limnersed in a pH buffer - 14 solution 37. The measuring electrode 10 is surrounded by a tube 21 of wall material having active (conductive) and inactive (non-conductive) regions 53, 54 respectively and produced as described above using a horizontal spinning process. The measuring electrode 10 is spaced from the tube 21 to provide an annular chamber 22 between the measuring electrode 10 and the tube 21. Therefore, the inner perimeter of the chamber is defined by the tube 11 of the measuring electrode while the outer perimeter is defined by the tube 21 of wall material.

A triple 0-ring seal 38 is provided between the measuring electrode tube 11 and the tube 21. The triple 0-ring seal 38 is located between upper and lower radial protrusions 39„ 42 respectively in the tube 11. The protrusions 39, 42 prevent slippage of the triple 0-ring seal 38. The annular chamber 22 in the region above the 0-ring seal 38 contains a full silicone potting material 43. The silicone potting material 43 is a sealant which is resistant to heat shock. The potting material 43 together with the triple 0-ring seal 38 expands and contracts as the temperature of the material increases and decreases and is resistant to heat shock.

Radially outwardly of the tube 11 and between the protrusion 42 and the triple 0-ring seal 38 there is an annular air chamber 44. The annular chamber 22 is filled with gelled electrolyte 45 below the air chamber 44. The annular air chamber 44 provides an air space for the expansion of the silicone potting 43, the electrolyte 45 and the triple 0-ring seal 38 when the electrode is exposed to high temperatures.

An Ag/AgCl reference cell 46 is immersed in the gelled electrolyte 45. A contact wire 5 extends upwards from the reference cell 46 through the triple Oring seal 38 and the silicone potting 43 and from the annular chamber 22 to connect the electrode to a coaxial cable which leads to a measuring instrument when in use.

The electrolyte 45 is sealed within the chamber 22 by a lower 0-ring seal 47 between the tube 11 (at the base of the non-ion responsive glass region) and the tube 21. The 0-ring seal 47 is - 15 maintained in position by a protrusion 72 on the measuring electrode located above the pH/pX responsive bulb 12.

Internally, the measuring electrode 10 has a similar air-space and potting material arrangement to that of the chamber 22. Approximately halfway along its length the glass electrode contact wire 13 is surrounded by an internal glass tube 49 which forms a fully annealed Pt/glass seal about the contact wire 13.

A second triple 0-ring seal 48, similar to the one previously described, is provided between the internal glass tube 49 and the tube 11. The tube is filled with full silicone internal potting material 43 above the 0-riag 48 as previously described while the tube 11 also has an internal air chamber 51 below the second triple 0-ring seal 48. Below the air chamber 51„ the tube 11 is filled with the pH buffer solution 37 as previously described.

The tube 21 is made up of conductive region 53 at its lower end adjacent the Ag/AgCl cell 45 and a non-conductive region 54 which makes up the remainder of the tube 21. The tube 21 is manufactured as described in Example 3.

In the conductive region 53 the salts contained within this region are concentrated on the outer surface of the tube 21 due to the horizontal spinning process as indicated by the reference numeral 50. As indicated above, a higher concentration of salts on the outer surface of the tube 21 facilitates electrical contact with the solution and improves the performance of the electrode. Furthermore, conductive regions of the tube 21 are more hygroscopic than those of nonconductive regions. Hygroscopic regions adjacent electrical contacts can result in errors. The electrode of the invention is connected to a measuring instrument (not shown) at electric contact regions indicated by the reference numeral 74. Therefore, the use of the nonconductive region 54 adjacent the electric contact regions 74 of the electrode reduces signal and reading errors.

Figure 7 shows a diagrammatic longitudinal cross-section through a combined reference electrode-measuring electrode assembly which is - 16 also combined with a thermocompensator 55. The electrode is made up of a cylindrical plug or block 56 of conductive wall material manufactured as described above. The electrode has a standard measuring electrode 10 similar to the ones previously described extending longitudinally through the center of the block 56. The pH/pX responsive bulb 12 of the measuring electrode 10 protrudes from the base of the block 56 into a recess 51 defined in the bass of the block 56. The measuring electrode 10 is maintained in a fluid tight relationship with the block 56 by a lower triple 0-ring seal 57 surrounding the measuring electrode 10 adjacent the recess 51 and an upper triple 0-ring seal 58 surrounding the measuring electrode 10 at the upper surface of the block 56.

The therraocompensator 55 is inserted into the conductive block 56, The thermocompensator 55 is a standard thermoconipensator made up of a first pole 59 and a second pole 60 which are connected to a measuring instrument. An Ag/AgCl reference cell 46 is also inserted in the block 56. The reference cell 46 is similar to the ones previously described in 'that it contains a Pt/glass seal 62 and a contact wire 5 and an electrode element 61 is inserted into a KC1 gelled electrolyte 63. At its base, the Ag/AgCl reference element is provided with cotton wool wadding 73 through which the reference element 61 makes conductive contact with the block 56 and thus with the solution in which the electrode is inserted.

The conductive block 56 functions as a salt bridge so that the use of wood and teflon junctions is avoided and a hardwearing resilient combined thermocompensator, measuring and reference electrode is produced.

Figure 8 shows a diagrammatic longitudinal cross-section of an alternative embodiment of a combined reference electrode-measuring electrode assembly also combined with a thermocompensator 55. As shown in the drawing, the combined reference electrode-measuring electrode assembly is also made up of a block 56 of conductive polymeric wall material which is statically moulded into the desired shape as described above. The block 56 also has a recessed base 51 and defines an open topped internal cylindrical chamber 64. A - 17 measuring electrode 10 extends longitudinally through the chamber 54 and into the recess 51 as previously described. A chloridised silver cylinder 55 is mounted in the chamber 54 and surrounds the measuring electrode 10. The silver cylinder 56 is spaced apart from the conductive block 56 by a double 0-ring seal 67, 58 respectively to provide an annular chamber 69 between the silver cylinder 66 and the conductive block 56. The annular chamber 69 is filled with a gelled silver saturated KC1 electrolyte 70, The silver cylinder 66 together with the gelled electrolyte 69 function as an Ag/AgCl reference cell which makes contact with a sample solution through the conductive block 56.

The thermocompensator 55 can be inserted through an opening 71 provided therefor in the measuring electrode J.0 An advantage of the present embodiment of a combination electrode together with thermocompensator is that the electrode can be easily assembled and a more efficient seal can be provided through the use of the double 0-ririg seal 67, 68 and the silver cylinder 66. The 20 use of the silver cylinder 66 also provides a more stable reference signal for the reference cell while the non-pemsable conductive block 56 prevents sample solution contamination.

Figure 9 shows a diagrairanatic longitudinal partial cross-section 25 of the electrode assembly of Figure 7 in a casing of inert plastics material or glass which is not electrically conductive, with the measuring electrode 10 in a recessed position while Figures 10 and 11 show diagrammatic longitudinal partial cross-sections of the combined reference electrode-measuring electrode assembly with the measuring electrode 10 in protruding and notched positions respectively. As shown in Figure 9, the block of conductive material 56 has a recess 51 in its base and is housed in a casing 99. The conductive block 56 is maintained in a fluid tight relationship with the casing 99 by means of a quadruple 0-ring seal 100. The measuring electrode 10 protrudes into the recess 51 defined by the block 56. In this embodiment, the measuring electrode is protected by the casing 99 and the conductive block 56 so that the assembly is particularly suitable for the analysis of high-velocity and/or high-density solids.

In Figure 10, the measuring electrode 10 protrudes from the conductive block 56. In this embodiment, the conductive block 56 is also housed within a casing 99 as described above. However, the conductive block 56 is not recessed but is flush with the end of the casing 99. The flush arrangement is particularly suitable where fouling of the measuring electrode 10 is expected as the conductive material provides extra protection for the electrode.

Figure 11 shows the measuring electrode 10 located within a notch 101 defined by the conductive block 56. The conductive block 56 is once again housed in the casing 99. However, in the present embodiment the conductive block 56 protrudes from the casing 99 in the form of a notched form with the measuring electrode 10 recessed in the notch 101. Therefore, the conductive polymeric material extends beyond the liquid junction surface of the Measuring electrode 10 to provide protection for the electrode. This arrangement is particularly suitable for submersible sensors.

Figure 12 shows a diagrammatic longitudinal partial cross-section through a block reference electrode assembly 75 similar to the reference electrode assembly of Figure 1. As sho,r>i in Figure 12, the block reference electrode assembly 75 is made up of a cylindrical block of conductive polymeric wall material 76 contained in a cylindrical container 77 open at the top. The upper surface of the cylindrical block is provided with three recessed cups 78, 79, 80 formed using a static moulding process. A reference electrode as shown in Figure 1 is mounted horizontally within the block 76 beneath the cups 78, 79, 80. However, in the present embodiment, the conductive material of the cylindrical block 76 replaces the tube 1 illustrated in Figure 1. The reference electrode is connected to a measuring instrument to which a pH/pX measuring electrode (not shown) is also connected.

Each of the cups 78, 79, 80 can perform a different function in use. For example, the cups 78 and 80 can be used as pH buffer cups and the cup 79 can be used as a sample cup. The cups can be steam sterilized between applications. - 19 In use, pH calibration buffers can be inserted into the pH buffer cups 78 and 80 while a sample solution can be inserted into the sample cup 79. A user works with a single pH/pX measuring electrode which can be calibrated using the pH buffer cups 78, 80 in use and can also measure the pH in the solution in the sample solution cup 79 all measurements being taken with reference to the reference electrode 72 with which each cup 78, 79, 80 is in electrical communication via the block 76. The present embodiment has particular applications in micro-sampling measurements and also in the sampling of solutions with high concentrations of protein which can result in precipitation between Ag/AgCl solutions and proteins which clog porous liquid junctions in standard electrodes.

The present embodiment has the advantages that the measuring electrode can be quickly calibrated between sampling measurements, the reference electrode enjoys a uniform and large contact area with each of the cups, and the block 76 can be steam sterilised between applications thus making the arrangement particularly suitable for micro-applications e.g. measurements of protein containing solutions.

Figure 13 shows a reference electrode cell of the invention for use in High Performance Liquid Chromatography (HPLC systems).

As shown in Figure 13 „ a reference electrode cell of the invention suitable for use in High Performance Liquid Chromatography is made up of a miniature reference electrode 95 which is insertable in a High Performance Liquid Chromatography device.

The miniature reference electrode 95 is made up of a miniature Ag/AgCl reference cell 96 inserted in a block of conductive polymeric wall material 97. The reference cell 96 is made up of an open-ended glass tube 106 containing electrolyte 108 a cotton wool plug 105 and an electrode element 109. The conductive material and the Ag/AgCl reference cell 96 are both housed in a suitably shaped open topped cell body 102 adapted to be insertable in a HPLC device. The conductive block 97 is formed to define a flowthrough passage 98 through its centre having an inlet 103 and an outlet 104. A sample is passed through the reference electrode from a HPLC column via the - 20 inlet 103 and outlet 104 as indicated by the arrows. The electrode functions in a manner analogous to the flow through cell illustrated in Figure 4 above.

The attached claims broadly define the invention. However, the invention also extends to a reference electrode in which the polymeric material is in tubular form which has been created by moulding. Preferably, the tubular form has been created by horizontal spinning during curing. Suitably, the tubular form has electrically conductive 10 and electrically non-conductive regions.

Alternatively, the invention provides a reference electrode for use in monitoring flowing solutions wherein a flow-through reference electrode is provided comprising a tube of the electroconductive wall 15 material whose internal surface defines the passage through which the sample solution can flow, and a housing radially outward of said tube, the tube and housing defining an annular chamber to hold electrolyte, and an electrode element housed in said chamber.

In an alternative embodiment the invention provides a reference electrode combined with a measuring electrode to form a single-unit electrode assembly wherein the measuring electrode is fitted inside a tube of the electroconductive material so as to define an annular chamber between them to hold electrolyte, with the measuring electrode 25 as the radially-inner wall and the tube of electroconductive material as the radially outer wall of the chamber, and an electrode element housed in said chamber.

The invention also provides a reference electrode combined with 30 a measuring electrode to form a single unit electrode assembly wherein the measuring electrode and the reference electrode are mounted in a block of the immobilized non-porous electroconductive polymer material.

In an alternative embodiment, the reference element of the reference electrode comprises an open-ended chloridised silver cylinder which forms at least a portion of one of the walls which define the electrode chamber. - 21 The invention also provides a reference electrode having quartz dispersed in a suitable amount in the wall material to reinforce the material.

The invention also extends to a method of making a polymeric material suitable for use as at least part of a salt bridge of a reference electrode which method comprises mixing from 35-55 parts by weight of one or more salts of potassium, sodium and/or lithium in powder form with from 57 - 37 parts by weight of an uncured polymer so as to disperse the salt(s) through the polymer, and curing the polymer to an immobilised non-porous body.

Suitably, the polymer is a vinyl ester resin and the salt is potassium chloride and the weight ratio of vinyl ester/potassium chloride is about 48/44.

Preferably, the method of making the polymeric material comprises mixing the one or more salts of potassium, sodium and/or lithium in powder form with an uncured polymer so as to disperse the salt(s) through the polymer, placing the mixture in a mould having a longitudinal axis, positioning the mould in an orientation such that the longitudinal axis of the mould is substantially vertical, allowing at least some of the salt(s) to settle in the mixture so that the salt concentration in the lower region thereof is increased relative to the upper region thereof, and curing the polymer to an immobilised non-porous body.

More preferably, the method comprises mixing the one or more salts of potassium, sodium and/or lithium in powder form with an uncured polymer to form active wall material, placing the active wall material in one region of a mould and placing inactive wall material comprising uncured polymer without the added salt(s) in another region of the mould having a longitudinal axis, positioning the mould with its axis substantially horizontal, spinning the mould about the longitudinal axis while curing the polymer to an immobilized non-porous body having an electrically conductive and electrically nonconductive region.

Claims (5)

1. A reference electrode for use with a measuring electrode for measuring ion activity in a sample solution, said reference electrode comprising: an electrode chamber for holding electrolyte in complete isolation from the sample solution, and an electrode element in said electrode chamber, wherein at least a portion of one of the walls which define said chamber is formed of wall material comprising an immobilised non-porous polymer having one or more salts of potassium, sodium and/or lithium mixed through at least one region of said wall material before curing of the polymer to render said region of the wall material electrically conductive, said wall providing a physical barrier between the electrolyte and the sample solution but permitting electrical communication between them.

2. An electrode assembly as claimed in claim 1 further comprising a thermocompensator.

3. A method or making a polymeric material suitable for use as at least part of a salt bridge of a reference electrode which method comprises mixing from 35-55 parts by weight of one or more salts of potassium, sodium and/or lithium in powder form with from 57 - 37 parts by weight of an uncured polymer so as to disperse the salt(s) through the polymer, and curing the polymer to an immobilised non-porous body.

4. A reference electrode, substantially as hereinbefore described with reference to and/or as shown in one or more of the accompanying drawings or with reference to one or more of the Examples.

5. A method of making a polymeric material, substantially as hereinbefore described with reference to and/or as shown in one or more of the accompanying drawings or with reference to one or more of the Examples.