Liquid junction flowing

Electrochemical methods covered in this chapter include poten-tiometry, coulometry, and voltammetry. Potentiometric methods are based on the measurement of an electrochemical cell s potential when only a negligible current is allowed to flow, fn principle the Nernst equation can be used to calculate the concentration of species in the electrochemical cell by measuring its potential and solving the Nernst equation the presence of liquid junction potentials, however, necessitates the use of an external standardization or the use of standard additions. 

However, in the case of stress-corrosion cracking of mild steel in some solutions, the potential band within which cracking occurs can be very narrow and an accurately known reference potential is required. A reference half cell of the calomel or mercury/mercurous sulphate type is therefore used with a liquid/liquid junction to separate the half-cell support electrolyte from the process fluid. The connections from the plant equipment and reference electrode are made to an impedance converter which ensures that only tiny currents flow in the circuit, thus causing the minimum polarisation of the reference electrode. The signal is then amplifled and displayed on a digital voltmeter or recorder. 

Fig. 5.5 SEM surface view and cross section of an electrodeposited, ca. 1 p.m thick, CdSe/li film subjected to accelerated photocorrosion by the apphcation of -0.1 V vs. Pt bias in polysulfide solution under a focused, high-power (1 W cm ) solar illumination for 30 min. The coherence of the as-deposited film morphology is evident. The authors emphasize that, even in this situation, the liquid junction nature prevents the flow of high leakage currents during the process (as it might be the case with a solid junction). (Reprinted from [99], Copyright 2009, with permission from Elsevier)...

The next focus is on the electrolyte-concentration cells with a liquid junction. The dilution of HC1, which was the subject of the discussion above, can also be realized in a cell with a liquid junction, as shown in Figure 6.13. It is presupposed that the two HC1 solutions of different concentration can be brought together and averted from mixing. The flowing of two streams of solution synchronously sometimes attains this. One then can establish the cell ... 

The emf of the cell can be related to the total reaction that takes place when 1 Faraday of current flows. The reactions which take place at the electrodes and those which take place at the liquid junction can be expressed separately. The electrode reactions are ... 

The algebraic sum of the individual electrode potentials of an electrochemical cell at zero current, i.e. cell = cathode + node. In practice, when current flows in a cell or a liquid junction is present (vide infra), and for certain electrode systems or reactions, the cell potential departs from the theoretical value. 

FIGURE 6 Schematic representation of different interfaces for chip CE-ESI/MS (A) spray directly from the chip, (B) liquid-junction capillary interface, (C) gold-coated capillary interface, and (D) coaxial sheath-flow configuration. Reprinted from reference 410 with permission from Elsevier Science B.V. 

While the Planck liquid-junction model corresponds to a junction with restrained flow , for example in a porous diaphragm, fig. 2.2, the Hendersoii model approaches a liquid junction with free diffusion (fig. 2.3). Ives and Janz [13] give inaccuracies in measuring liquid-junction potentials between 1 and 2 mV. 

Figure 4.20.A shows a more recent cell reported by Cobben et al. It consists of three Perspex blocks, of which two (A) are identical and the third (B) different. Part A is a Perspex block (1) furnished with two pairs of resilient hooks (3) for electrical contact. With the aid of a spring, the hooks press at the surface of the sensor contact pads (4), the back side of which rests on the Perspex siuface, so the sensor gate is positioned in the centre of the block, which is marked by an engraved cross as in the above-described wall-jet cell. Part B is a prismatic Perspex block (2) (85 x 24 x 10 mm ) into which a Z-shaped flow channel of 0.5 mm diameter is drilled. Each of the wedges of the Z reaches the outside of the block. The Z-shaped flow-cell thus built has a zero dead volume. As a result, the solution volume held between the two CHEMFETs is very small (3 pL). The cell is sealed by gently pushing block A to B with a lever. The inherent plasticity of the PVC membrane ensures water-tight closure of the cell. The closeness between the two electrodes enables differential measurements with no interference from the liquid junction potential. The differential signal provided by a potassium-selective and a sodium-selective CHEMFET exhibits a Nemstian behaviour and is selective towards potassium in the presence of a (fixed) excess concentration of sodium. The combined use of a highly lead-selective CHEMFET and a potassium-selective CHEMFET in this type of cell also provides excellent results.

The experimental apparatus consists essentially of a narrow vertical glass tube down the inner surface of which one liquid is made to flow, the other liquid emerges from a fine glass tip in the form of a narrow jet down the axis of the tube. The two solutions are connected with calomel electrodes employing potassium chloride or nitrate as junction liquids. The E.M.F. of the cell is measured by means of a sensitive quadrant electrometer. The greatest source of error in the method is the elimination of or the calculation of the exact values of the liquid-liquid junction potentials in the system. For electrolytes which are not very capillary active, the possible error may amount to as much as fifty per cent, of the observed E.M.F. 

Diffusion or liquid junctions are thus not clearly defined since the potential difference is dependent on the sharpness of the junction. Uniformly sharp junctions have been obtained by Lamb and Larson J.A.G.k XLii. 229,1920) by allowing one liquid to flow against the other, whilst Bjerrum f. Elektroohem. Liii. 428, 1906), has obtained a relatively diffuse junction by the insertion of a sand diaphragm between the two electrolytes. 

This cell has two electrolytic solutions, aqueous CuS04 and aqueous ZnS04, which are separated by a porous barrier. The barrier stops convective mixing of the two solutions. With the circuit open, there can be no net ionic flow through this barrier. However, ions of different size (e.g., Cu2+ and Zn2+) have different rates of diffusion through the pores of the barrier. A junction potential must therefore develop at the barrier to counter the tendency for diffusion to produce a net current. Liquid junctions are indicated by broken vertical lines in the cell... 

A test system, controlled by personal computer (PC), was developed to evaluate the performance of the sensors. A schematic of this system is shown in Figure 3. The signals from the sensors were amplified by a multi-channel electrometer and acquired by a 16 bit analog to digital data acquisition board at a resolution of 0.0145 mV/bit. The test fixture provided the electrical and fluid interface to the sensor substrate. It contained channels which directed the sample, reference and calibrator solutions over the sensors. These channels combined down stream of the sensors to form the liquid junction as shown in Figure 1. Contact probes were used to make electrical connection to the substrate. Fluids were drawn through the test fixture by a peristaltic pump driven by a stepper motor and flow of the different fluids was controlled by the pinch valves. 

Flowing junction — is a special kind of - liquid junction made in such a way that the two electrolyte solutions forming the junction are flowing in a vertical tube so that the upward flow of the heavier electrolyte meets the downward flow of the lighter electrolyte solution. Lamb and Larson have developed this type of liquid junction and they have discovered that the flowing junction gives... 

Due to the different mobilities, concentration gradients and thus potential gradients will be established. In actual measurements these potentials will be added to the electrode potentials. A calculation of liquid junction potential is possible with the -> Henderson equation. As liquid junction potential is an undesired addition in most cases, methods to suppress liquid junction potential like -> salt bridge are employed. (See also -> diffusion potentials, -> electrolyte junction, -> flowing junctions, and -> Maclnnes.)... 

IV. The Flowing Junction.—In order to obtain reproducible liquid junctions, in connection with the measurement of the e.m.f. s of cells involving boundaries between two different electrolytes. Lamb and Larson devised the flowing... 

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