Suggested Problems From S.H.C.

Potentiometry

Ch 23 :! Theory 23-1 to 23-7 Calc 23-15, -17, -19 & -26

Membrane potentials are responsible for the operation of the nervous systems of living organisms. Chemists make use of Membrane potentials to construct chemical sensors for various ions in aqueous solutions. Hydrogen, sodium, potassium, and fluoride ions are routinely determined by these sensors. The pH electrode is the most common membrane sensor. It uses a glass membrane to detect H+

Point of care monitoring. An example of the application of potentiometry

?
* * * * *

* Measured using Potentiometry

When blood ow to part of the heart is interrupted, potentially lethal changes in ionic concentrations occur. To study such an event, chemists, engineers, and doctors pooled their knowledge to create exible, miniature ion-selective electrodes that could be inserted into a beating heart.

Fabrication of the device required photolithographic techniques from the microelectronics industry and polymer know-how to produce a mechanically exible end product. Adhesion of the various layers to one another was a signicant challenge in making a practical device.

In this device, four dots are sensors for K+ and four are sensors for H+. The dot at the front tip is a Ag / AgCl reference electrode for the eight sensors. The sensors have a linear pH (4 -12) and K + (10-1 to 10 -5 M) response.

Equipment required to do Potentiometry

High-input impedance voltmeter Reference Electrode Saturated Calomel Electrode (SCE) Silver/Silver Chloride Electrode Indicator Electrode Direct (Galvanic) electrodes Membrane electrodes (Ion-selective) Indirect electrodes

Silver/Silver Chloride Reference Electrode

AgCl(s) + eAg(s) + Cl- (satd)

Calomel (Hg2Cl2) Reference Electrode

Hg2Cl2(s) + 2e2Hg(s) + 2Cl- (satd)

E = 0.197 V
Notice that the internal solution is SATURATED in Cl-

E = 0.244 V

Analytical pH Measurement
Volts

Potentiometry: Ion-selective Electrodes

An ISE is an electrochem. half-cell (galvanic cell) in which the voltage varies with the activity of a specic ion. The specicity is due to a membrane that separates the solution to be measured from an internal lling solution. The voltage arises across the membrane.

Potentiometry: ISEs
Types of Ion Selective Electrode (based on membranes) 1. Glass membrane - pH electrode 2. Solid state (crystal) membrane a. Single crystal mobility type b. Solubility type 3. Liquid membrane 4. Indirect electrodes
Inside Electrode
X+ X+
A2 A! 2

Membrane X+ A!1 X+ A1

Outside the Electrode (Solution to be measured)

ISEs - How do they work?

Fundamentally different from metal electrodes (like the Ag+/AgCl electrode) in that ion-selective electrodes do not depend on redox processes. Key feature of an ideal ISE: a thin membrane with which only the intended ion can interact. Other ions "cannot" interact with the membrane. Ion migration creates excess +ve charge on one side of the membrane & excess -ve charge on the other side. At some point, the excess charges prevent further migration.

The equilibrium electric potential difference (E) from ion migration is related to the difference in activity of the ion on the two sides of the membrane.

The free energy difference for a species at activity A1 on one side of the membrane and activity A2 on the other is given by:

! G = " RT ln

A'1 A'2

At steady state, free energy is also given by -zFE (z = charge): therefore.....

' A1 A1 ' " ! RT ln A2 A2

The ISE membrane voltage is given by ......

! zFE = ! RT ln

E = E* +

0.0591 log A1 z

Rearranging and using base-10 logs.

Where E * = !

given electrode

0.0591 log A2 is a constant for a z

E=

0.0591 A 0.0591 0.0591 log 1 = log A1 ! log A2 z A2 z z

Z is the charge on the measured ion including the sign!

Liquid Junction Voltages

ISEs
In theory, membrane electrodes can be used to make direct potentiometic measurements In practice, the existence of liquid junction voltages REQUIRE ISE electrode calibration using std. solutions No electrode is truly selective. Other species (j) in solution can also interact with the membrane to produce a voltage......

When two electrolye solutions of different concentration are-brought in contact through a salt bridge a voltage develops across the bridge when ever the ions on the two sides have different mobility.

" % " $ zi ' % $z ' 0.0591 j& # E = E ' +! log$ ai + a j kij + ....' zi # &

The gure below is a segment of a calibration curve for a Ca2+ ionselective electrode at 25 C. We will assume ! is 1.0. (a) From THE CURVE estimate the value of [Ca2+] in an unknown sample which gives a potential of -327.1 mV. (b) The selectivity coefcient for Pb2+ for this electrode for is 20. What % error would arise in the answer for part (a) if, unknown to the analyst, there was 6 X 10-8 M Pb2+ in the unknown sample.

E is the cell voltage E' is a constant for a given measurement established by calibration ! is a constant that depends on the electrode (close to 1) j is an ion that also interacts with the membrane z is the charge, INCLUDING THE SIGN on ion kij is the selectivity coefcient The kij is a measure of electrode selectivity for one species (i) over another interfering species (j) E includes all constant cell voltages (reference electrode voltages, junction voltages, and E*)

Part a. To begin, we need to calibrate the electrode by determining the value for E
E=E +
E =E!
'

Next we use the E value and the measured voltage to calculate the Calcium concentration:

'

0.0591 2+ log[ Ca ] 2
0.0591 0.0591 2+ log[ Ca ] = !0.280 ! !3.8 2 2

!0.3271 = !0.168 +

0.0591 log[ Ca2+ ] 2

= !0.280 ! (!0.112) = !0.168V

[!0.3271 ! ( !0.168)] 2 = !5.38 0.0591 [ Ca2+ ] = 4.13 " 10!6 M log[ Ca2+ ] =

b. The interferent equivalent activity is given by the product of the selectivity coefcient and the real interferent activity.

Interferent equivalent concentration: 20(6.0 x 10-8) = 1.2!x!10-6 M

"Real" Ca 2+ concentration : 4.13 x 10 -6 M - 1.2 x 10-6 M = 2.93 x 10-6 M

The glass electrode cell (pH meter) is usually a two-electrode cell containing a reference electrode on each side arranged as follows: Ag/AgCl(s),Cl-(aq),H+(aq)/glass/test soln (H+)//Cl-(aq),AgCl(s)/Ag pH Electrode Ref. Electrode

Glass Membrane

Crystal-Membrane Electrodes
(e.g.Fluoride)

Solubility type ISEs:

Based on a membrane using the very insoluble salt Ag2S (Ksp!= 10-51 )

Membrane is a single lanthanum fluoride crystal doped with europium fluoride. 100% selective for F- ions. OH- interference (reacts with the lanthanum to form La(OH)3, releasing extra F- ions. Eliminate interference by adding a pH buffer to the samples (pH 4 to 8) to ensure a low OH- concentration.

Ag2S (s)

2 Ag+

S2-

The electrode is sensitive to both Ag+ and S2Electrodes sensitive to other ions can be constructed using mixed insoluble salts: For halide electrodes and SCN- use AgX - Ag2S mixtures where X = Br, Cl, F, I, SCN. For heavy metal electrodes use MS mixtures where M = Pb, Cu, and Cd

Impregnated-PVC-Membrane Electrodes (e.g. Potassium)

Membrane is a thin disc of PVC impregnated with the macrocyclic antibiotic valinomycin. This compound has a hexagonal ring structure with an internal cavity ~ the same size as K+. It complexes with K+ and preferentially conducts it into the membrane. Not 100% selective - can also conduct sodium and ammonium ions.

Urea Selective Electrode

- an example of an indirect electrode

NH4+ electrode Semipermeable membrane Urease CO(NH2)2 + 2 H2O 2 NH4+ + CO32-

Dissolved gas electrode for CO2

another indirect electrode.....

Some applications of ISEs

Pollution Monitoring:
CN-, F-, S2-, Cl-, NO3- etc., in effluents, and natural waters.

Agriculture and Food:

NO3- , Cl-, NH4+, K+, Ca2+, I-, CN- in soils, plant material, fertilisers and feedstuffs. F- in drinking water and other drinks. Ca2+ in dairy products and beer. K+ in fruit juices and wine making. Orion makes wine measurements quick and easy with the new Wine Master. Wine Master provides everything needed for accurate measurement of percent alcohol, sultes, acidity, sugar, pH or temperature, with easy to follow step by step instructions. The Advanced 950W offers the convenience of an automatic dispenser eliminating any operator errors. The affordable Basic 720W offers a manual dispenser allowing for operator control of solution addition With Wine Master, make wine measurements for a fraction of the cost of sending wine samples to a lab.

Paper Manufacture:
S2- and Cl- in pulping and recovery-cycle liquors.

Electroplating:
F- and Cl- in etching baths; S2- in anodising baths.

Biomedical and Clinical Laboratories:

K+, Ca2+, Cl-, in body fluids (blood, plasma, serum, sweat). F- in skeletal and dental studies.

Advantages of ion-selective electrodes.

1) When compared to many other analytical techniques, IonSelective Electrodes are relatively inexpensive and simple to use and have an extremely wide range of applications and wide concentration range. 2) The most recent plastic-bodied all-solid-state or gel-filled models are very robust and durable and ideal for use in either field or laboratory environments. 3) Under the most favourable conditions, when measuring ions in relatively dilute aqueous solutions and where interfering ions are not a problem, they can be used very rapidly and easily (e.g. simply dipping in lakes or rivers, dangling from a bridge or dragging behind a boat). 4) They are particularly useful in applications where only an order of magnitude concentration is required, or it is only necessary to know that a particular ion is below a certain concentration level (semi-quantitative analysis).

5) They are invaluable for the continuous monitoring of changes in concentration: e.g. in potentiometric titrations or monitoring the uptake of nutrients, the consumption of reagents, or point of care monitoring. 6) They are particularly useful in biological/medical applications because they measure the activity of the ion directly, rather than the concentration. 8) With careful use, frequent calibration, and an awareness of the limitations, they can achieve accuracy and precision levels of 2 or 3% for some elements and thus compare favourably with analytical techniques which require far more complex and expensive instrumentation. 9) ISEs are one of the few techniques which can measure both positive and negative ions. 10) ISEs can be used in aqueous solutions over a wide temperature range. Crystal membranes can operate in the range 0C to 80C and plastic membranes from 0C to 50C.