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Lab Experiment #2
2-5-II
electrical resistance (50,000 vs. 100,000 resistance for glass membranes), thus improving
conductivity. The electrode has excellent selectivity, OH- being the main interference(selectivity
constant = 0.1). Pure rare earth fluorides have a high electrical conductance because fluoride ions
are mobile in the crystalline lattice. He crystal membrane is permeable only to fluoride ions, so
the cell potential(E) can be determined by the Nernst equation:
E = E + RT/F ln a F-
where the value of E depends on the choice of internal and external reference electrodes and the
fluoride activity in the internal electrode solution.
composition of the sample except for a small liquid-liquid junction potential contribution.
Ideally, the electrode will be selective for fluoride ions over ranges in sample composition
where the crystalline lanthanum fluoride membrane is stable. Because crystalline lanthanum
fluoride has a low solubility(Ksp = 10-29), the electrode can be used over a wide pH range. It can
also be used in the presence of many complexing agents.
There are many problems that can occur to produce errors in measurement when using
ISE. These include clogged junctions, breakage, gel layer, organic solvents, protein solutions,
errors in wiping electrodes, paints, dyes, and suspended solids, large potassium chloride crystals,
low slope, and having a dried electrode. Solutions of these problems are listed as follows:
Clogged Junctions
Increasing response time and drifting are symptomatic of a clogged junction, often
as a result of precipitated silver chloride (AgCl). Eighty percent of pH/ISE
measurements are in error due to this one problem, especially when using an
Ag/AgCl reference system. Soak these reference electrodes in saturated potassium
chloride (KCl; 4.07 M) in which any precipitated AgCl is 500X more soluble than
in distilled water. Heating a clogged junction in saturated KCl at 60C for 30
minutes may help. Calomel electrodes are designed to use saturated KCl (without
AgCl) and hence do not clog from within. Corning has designed a replaceable
Junction (477269) for cases where blocked junctions cannot be cleared.
Breakage
Nine of the new Corning electrodes have a see-through plastic body to minimize
breakage. Furthermore, the new protective guard feature protects the glass pH
bulb and can be removed for easy rinsing. Replace wetting caps between
measurements. DO NOT place electrodes in boiling water - they will crack.
Gel Layer
Longer response times will occur when frequent measurements are made in
alkaline and phosphate samples that cause the gel layer to slowly deteriorate.
Storage in 0.1 M KCl will avoid this problem. Avoid water absorbing solvents that
dehydrate the gel layer (see No. 4 below).
Organic Solvents
Non-aqueous solvents have a tendency to dry out the glass of the pH electrode
surface. Storage or soaking in a pH 7.00 buffer overnight will rehydrate the glass
surface. Test solutions should be more than 50% water. Remove the electrode once
the reading is stable.
Proteins Solutions
Longer response times will also occur when frequent measurements of made of
proteinaceous solutions. Other symptoms include low slopes. A soaking in solution
of 10% pepsin diluted dropwise with a 1.0 M hydrochloric acid (HCl) solution to a
pH of 1-2 will remove this coating from an electrode in a few hours. Apply soaking
solution as needed.
Wiping Electrodes
Wiping electrodes with paper will result in static charges building up on the surface
of their glass bodies. This will require time to remove these charges when placed in
samples and will result in fluctuating or erroneous readings. This problem is
especially common in dry areas during winter.
Paint, Dyes, Suspended Solids
Rinse a dirty electrode alternately with a solvent for the contaminating material,
then distilled water. A reverse sleeve electrode will produce a faster flowing
junction and prevent clogging by syrupy liquids.
Large Potassium Chloride (KCl) Crystals
Build-up of KCl crystals in a calomel electrode indicates the fill solution needs to
be changed. These crystals can block the flow through the ceramic junction.
Eliminate the crystals by replacing the fill solution. Draw off old fill solution with a
syringe or capillary pipette. Rinse twice with warm deionized water and once with
saturated KCl, then fill with fresh saturated KCl.
Low Slope
Etch the electrode with a solution composed of 2.0 g potassium fluoride (KF) in
98 mL H20 to which 2.0 mL concentrated H2SO4 has been added. Store this
solution in a plastic bottle and mark "hazardous". Wear gloves when etching. To
etch, place the electrode in the etching solution for only 20-30 seconds. Rinse
electrode with deionized water and soak in 7.0 buffer overnight.
Dried Electrode
A dry electrode is a dead electrode. Place the electrode tip into a wetting cap that
is full of 4 M KCl. Rehydrate glass electrodes for 24 to 48 hours in buffer 4.01
after prolonged dry storage.
Apparatus
Material
Quantity
pH Meter
Glass-calomel pH electrode
Fluoride-ion electrode
14
14
Pasteur Pipet
Reagents
Solution
Concentration(s)
Sodium Fluoride
Deionized Water
--
--
NaBr
0.1M
NaCl
0.1M
Electrode handling between samples - The electrode pair (the ISE and the reference electrode)
may be rinsed with distilled water and blotted gently to prevent cross contamination between
samples. Rinsing the electrode pair with the next solution is preferable, since it avoids the
necessity of wiping the electrode, thereby eliminating the possibility of scratching the sensing
element surface.
Storage - The halide electrodes can be stored dry without affecting their response. The electrodes
should be cleaned before storage to insure that residues of dilute solutions containing interfering
ions do not become concentrated by evaporation on the electrode sensing element.
Procedure
1-Transfer about 25 ml of 1.00e-5M fluoride stock solution into a 150 ml beaker
2-Carefully insert the pH electrode system and the F- ion electrode system into the solution and
adjust the pH to within 0.2 pH units of the desired value by adding a small amount of HNO 3 or
NaOH from a Pasteur pipet.
3-Measure the potential of the F- ion electrode