3.

COULOMETRIC TITRATIONS
In a coulometric titration the titrant is generated electrochemically by constant current from a proper
electrolyte. Coulometrictitrations are in many ways similar to volumetric titrations: the concentration of
the titrant is equivalent to the generating current, and the volume of the titrant is equivalent to the generating
time. The two modes are exemplified with an argentometric titration (Fig.3-1).
Generating
electrode:
Counter
electrode:

Fig.3-1 Titration of chlorides with Ag+: (a) volumetric,
(b) coulometric.
Coulometric titrations have numerous advantages:

Coulometric vs Volumetric Titrations
Coulomet Volu
ric
Preparation of standard solutions

None

Y

Standardization of titrant

None

Y

Storage of titrant

None

Y

Trivial

Diff

Trivial

Pos

Dilution effects during titration

None

Y

Addition of microquantities of analyte

Trivial

Diff

Determination of microamounts of analyte

Yes

Diff

Determination of microvolumes

Yes

Diff

Accuracy of titration

High

O

Economy of reagent

Maximal

Dep

Automation

Perfect

Pos

Remote control

Perfect

Pos

Use of labile
reagents
free KOH

End-point detection

or NaOH titrants

Same for both mod

Price
3.1. Electrogeneration of titrant
The basic requirement of a coulometric titration is 100% current efficiency of titrant generation.

In the table below several options for electrogeneration of titrant are presented. The most
straightforward options are those in which the titrant is produced as a result of (i) dissolution of electrode
material or (ii) decomposition of the solvent at an inert electrode. The reagent precursor in those cases is
present at infinitely large amounts.

Similar

the reagent precursor has finite concentration. a constant amount of electroactive material reaches the electrode and the plots are time independent. remains stagnant. taking place at the generating (working) electrode. the generation of titrant should be the only process. The rigorous mathematical analysis of mass transport in stirred solutions is a complex task. At potentials around +1. a larger current density is applied. The problem is evident .2.takes place.Sources of electrogenerated titrant Electrode material Solvent Reagent precursor In a large number of coulometric titrations. at more positive potentials water is oxidized. 60 m M HClO4 and 0. introduced by Nernst.the current efficiency of the generation of Br2 is not 100% any more. The oxidation of Br. An additional 2. The concentration profile of the electroactive species in stirred solutions. say 7. Area of the electrode: 0. according to the Nernst approach. Note: For 100% current efficiency: ig < il Fig. According to Nernst approach. Estimation of the maximal generating current when reagent precursor is used The amount of precursor reaching the electrode is determined by the rate of mass transport.Away from it the solution is in motion and uniform in concentration. If.3-2) obtained in stirred solution containing 10 mM KBr. bromide is added as precursor. . If this condition is not maintained. but adequate for a rough estimation. For example.1 M KNO3. however. The thickness of the layer remains unchanged with time. using the concept of diffusion layer. To ensure 100% current efficiency. If the current forced through the electrodes corresponds to a current density lower than that value. in order to generate bromine as titrant. however. adjacent to the electrode.3-2).5 mA/cm2 (dotted line (2) in Fig. 3. Due to the stirring of the solution.5 mA/cm2 (dotted line (1) in Fig. which is controlled by the concentration of the precursor. say 2.3-2 Experimental currentpotential curve for oxidation of bromides at a rotating disk electrode. This will be exemplified by a current-potential curve (Fig. is presented in Fig. the only reaction that takes place is the oxidation of bromide.can proceed at a maximum current density of 5 mA/cm2. a layer of thickness (the Nernst diffusion layer).0 V vs SCE the oxidation of Br. only 5 mA/cm2 are contributed by the oxidation of Br-. We shall proceed by a simplified approach. the intensity of stirring and the cell geometry.3-2).16 cm2. The mass transfer in the Nernst layer proceeds by diffusion and the concentration gradient is linear. The current by which the titrant is generated has to be smaller than the limiting current of the electrode process of interest.3-3. some unwanted electrode process could take place and bring to the reduction of the current efficiency. Proper choice of those parameters is of paramount importance for ensuring 100% current efficiency. Rotating rate: 400 rpm. Composition of solution: 10 mM KBr.5 mA/cm2 are due to the oxidation of water. The model is rather primitive. Auxiliary lines (1) and (2) are referred in the text.

4. and the lower . where C(x=0) = 0. as stated Fig. The generating current. The Nernst diffusion layer. is: · independent of time · inversely dependent on square root of stirring rate The flux of the electroactive species at the electrode surface is given by Fick's first law (1) where C* and C(x=0) are the bulk and surface concentrations of the electroactive species and D is its diffusion coefficient. Titrimetric Methods of Analysis). is dependent on the geometry of the cell. the current for which is independent of the above mentioned geometric parameters. Thus. 4 Limiting current density in stirred as function of concentration of precursor. Thus. as function of concentration of precursor. (The upper value is limited by the appearance of vortexes. (4) where is the rotating rate in Hz.3-4 provides an estimation of values of the current density at different rates.. . The corresponding current is (2) A limiting value of the current. il in A. In titrimetric analysis bar-stirred solutions are used. are displayed in Fig. 3.3-4.1200 rpm. Then (3) The thickness of the Nernst diffusion layer. concentration of precursor and area of working electrode Plots of limiting current density. il. for D = 10The right axes corresponds to the recommended current density at the generating electrode for a coulometric titration.3-2 and Fig. Considering the cell presented in Fig. effective stirring is achieved by rotating the magnetic stirrer in the range of 400 . calculated according to eq. C*. C* in mol/cm3.3-5) to a rotating disk electrode.4. No exact analytical expression is available for a bar-stirred solutions and can be estimated only experimentally by measuring il at a given bulk concentration. Furthermore.3solutions 5 cm2/s. the electrode arrangement and the distance between the bar and the electrode. and D in cm2/s. Analytical expression for il at a rotating disk electrode has been derived. is inversely proportional to the square root of the intensity of stirring. . 3-3 Nernst model of mass transfer in stirred solutions. of electroactive species. Optimal values of generating current.1-7 (cf. equivalence in currents compared to rotating electrode is needed.ensures that theelectrogenerated titrant has the chance to encounter virtually all the analyte within the time of about 100 s needed to reach the equivalence point in a continuous titration). .Fig. The limiting currents obtained under these conditions are approximately equal to those observed when the electrode itself is rotated at the same rate. j = il /A. the limiting rotating above. is reached at sufficiently large potentials. Fig. calculated according to eq. we refer in our examples (Fig.3.

for . the respective concentration of precursor should be 50 to 13 mM.. it is preferable to use a non-isolated counter electrode. There are several reasons for incompatibility: The product of the reaction between the analyte and titrant is restored at the counter electrode to the initial form of the analyte. Fe3+. however.. the passed current is limited to 50 mA.5 Coulomb and it is desired to accomplish the titration in 100 s. however. 3. e. Thus. if the total amount of charge needed to reach the equivalence point is 0. The main product at the counter electrode reacts with the analyte or with the electrogenerated titrant.4. a generating current of 5 mA is to be used.g.should be lower than the limiting current of the precursor in order to ensure 100% current efficiency. The electrogenerated titrant reacts at the counter electrode. 3. eq. (ii) incomplete isolation of the counter electrode will affect the accuracy of the titration. titration of Cl with electrogenerated Ag+..5 provides a guide for determining the experimental parameters: area of generating electrode and concentration of precursor. thus the possibility of the working electrode being located in a region of reasonably low stirring rate (400 rpm) should be considered. e. which did not have the chance to react with Cl-. titration of H+ withelectrogenerated OH-. nullifying the titration process. Counter electrode In many cases the reaction at the counter electrode is not compatible with the reaction of interest. be taken to ensure 100% current efficiency.5. An accepted solution for all these problems is isolation of the counter electrode. with n = 1). If the rate of rotation were decreased to 400 rpm. are lost by being reduced at the counter electrode. Models for non-isolated counter electrodes There are several approaches in devising non-isolated counter electrodes. since most coulometers operate under 40 V. (iii) it is unsuitable for automation and miniaturization.g. For example. For example. The difference may be related to differences in degree of stirring. we use a safety factor of 2). ig.5 instead of 0. This. if a titration is carried out at 20 mA/cm2.3-4) is (5) where n is the number of electrons involved in the electrogeneration of the titrant. titration of Fe2+ with Ce3+ as precursor.. The product of the electrode reaction at a non-isolated platinum counter electrode (H+) counterbalances the product at the working electrode (OH-). The generating current is chosen considering the amount of analyte and a reasonable time for the titration to be accomplished. Care must. Solubility limitations or price of the precursor may dictate the choice for the electrode area. imposes experimental difficulties: (i) the solution of the counter compartment has to be replaced frequently. A well-designed experiment should ensure successful results also in less favorable conditions.2. e. Thus. (a) Creating conditions at which an undesired process is prevented by limiting the potential of the counter electrode.5 is given by Lingane1: 0. Silver ions.g. is reduced to Fe2+ at a non-isolated Pt counter electrode.3-4).3-4 can be used to determine the concentration of reagent precursor for a given current density at the generating electrode or vice versa. for a reasonable value of the area ranging from 0. Note: If the resistance between the generating and the counter electrodes reaches . only 10 mA/cm2 could be passed at the same concentration without affecting the current efficiency. in these conditions (Fig.5 to 2 cm2. A safety factor of 2 is used in estimating the recommended current density at a generating electrode in coulometric titrations (right axes of Fig. The generating current. Furthermore. Eq. . (iv) it substantially increases the resistance between the electrodes. Fig.5. the lowest concentration of the precursor that can be used is ~60mM. the product of the titration. Lingane refers to "well stirred solutions" and we refer to moderate stirring. The product Cprec (mM)·Ag (cm2) should be at least 25 (cf. (A different coefficient for eq.

AgX43-. since the solubility of AgBr is the lowest. A general solution is presented here4. which allows us to estimate the mass transport limited current in stirred solutions (eq. 0. that the concentration of Br.Leiser. Keeping the concentration of the titrant in the solution as low as possible. 0. Each of the above points is treated below. One of the problems resulting from the use of non-isolated counter electrodes is that the electrogenerated titrant can react at it instead of reacting with the analyte. Chem. The total concentration of the dissolved species as function of concentration of halide is given in Fig.1 M KNO3. Anorg. Replacing the platinum electrode with silver.3 is an elegant solution for the titration of H+. It is advisable.3-5).3-6 Solubility of silver halides in sodium halide solution at 18oC (K.be not higher than 50mM. At AgRDE: 2 mM HCl. which need to be modified: Decreasing the area of the counter electrode. Fig.. (Reduction of Ag+ would reduce the titration efficiency). The basic principle is to render mass transport of the titrant at the counter electrode negligibly small by modifying the factors involved.has to be controlled due to the formation of soluble complexes AgX2.H. Consider for this purpose the Nernst approach. Simple analysis of the equation shows the parameters.. which isolates electrically the electrode.Allgem. Using an electrode geometry for which il will be minimal.3). The composition of the solution is modified by adding excess of a halide salt. otherwise the life span of the electrode is shortened more rapidly by the formation of a thick layer of AgX precipitate. The size of the counter electrode should be not smaller than that of the generating electrode.35 Currentpotential relationship at rotating disk electrodes (platinum and silver) at 400 rpm. the anodic decomposition of water is prevented (Fig. bromides are most suitable.formed at the generating electrode is counterbalanced by the H+ formed at the counter electrode.1 M KNO3 and 10 mM KBr. 292.3-6. At PtRDE: 2 mM HCl. (b) Hampering direct reaction of the titrant at the counter electrode based on geometric and kinetic considerations. Fig.AgX32. Keeping the Nernst diffusion layer as large as possible. where in a two-platinum electrode cell the OH.. whose role is forming insoluble silver salt.The Ag/AgBr counter anode2. . 97 (1957)). thus preventing reduction of Ag+ at the cathode. 5-100 mM. Z. The excess of X. In the concentration range of interest.

a high current density of up to at least 100 mA/cm2 can be used. The higher the rate. This is somewhat contradictory to the requirement of efficient stirring. The increase in the rate of the chemical reaction is of importance not only with respect to the counter electrode.1-7). A small disk is better than a thin wire of identical area. Geometry of the counter electrode. even with less strict observation of the above mentioned conditions. The reaction between iodine and As(III) is very fast. For example.2 mM of each in 50% methanol) more than 200 s are required at 5 mM HClO4 and only 5 s at 50 mM HClO4. The optimal place to locate the counter is far away from the working electrode and from the magnetic stirrer. For the case where the main reaction at the counter electrode is the decomposition of the solvent.is titrated with a generating current of 5 mA.05 cm2 can be employed. Thus. in which none of the titrant reacts up to the equivalence point. Acidity and alcohol content are the most important factors. The flux of .Decreasing the area. high accuracy can be achieved with a non-isolated counter electrode. A worst case.and Hg(I) (mixing 0. A smallarea counter electrode (0. a counter electrode as small as 0. It is. Note: (1) Conditions for titration with : · strong acid (HClO4 or HNO3) · (2) Electrode reduction of at the counter electrode decreases the efficiency of the titration. the smaller the concentration of free reagent.4). i. efficient stirring throughout the solution can be reached at moderate rotation of the magnetic bar (400 . will be considered.600 rpm). 0. This represents 0. if a current of 10 mA is used in the coulometric titration.2% of the total current passed. A 1mM solution of Cl. however. and its average concentration up to the end point is half the initial concentration of the analyte. Low values of the instantaneous concentration of electrogenerated titrant in the solution can be achieved by: (i) Producing a uniformly distributed titrant by efficient stirring and using a large-area generating electrode. The only way to increase the Nernst diffusion layer at the counter electrode is to decrease the stirring rate in the vicinity of the counter electrode. and thus the smaller the chances for its reaction at the counter electrode. but also for the completion of the titration process in reasonable time.5 mM. leading to a 0.with electrogenerated Hg(I). the approach proposed above is a simple and elegant method for using a non-isolated counter electrodes for cases in which the electrogenerated titrant can react at the counter electrode. Keeping as large as possible. where the stirring is equivalent to 400 rpm of a rotating disk electrode. The above outlined principles will be tested with an example of constant-current titration of Cl. if a small cell with a volume of 5 . very difficult to determine the instantaneous concentration.05 cm2) is located in the upper layer of the solution.. Substituting this concentration in the Levich equation. Since the generating current is constant. Hg(I). It will be shown that only a negligibly small fraction of the titrant. (ii) Increasing the rate of reaction between the analyte and the electrogenerated titrant.10 ml is used (Fig. provided the instantaneous concentration of Hg(I) is known. For the completion to 90% of the reaction between Cl. the instantaneous concentration of Hg(I) increases linearly with time. one finds that the average rate of titrant loss correspondsto . In fact the error is much smaller since the basic requirement for a titration is a fast reaction between titrant and analyte. In conclusion. Thus. since the flux at the former is smaller. the rate of reaction between chloride and Hg(I) can be substantially changed by manipulating the composition of the solution.2% error at most. is lost by reduction at the counter electrode: The current of the electroreduction of Hg(I) can be estimated according to Levich equation (eq.e. Reaction of interest: Competing reaction: An additional example of successful application of the above principles is the titration of As(III) with electrogenerated iodine. However.

3. closed at both ends by porous membrane (sintered glass or ion-exchange membrane). The titration of Cl. Thirsty glass is a porous. with few exceptions. a plugged tube of Vicor brand thirsty glass (Corning 7930) effectively prevents mixing of the two solutions while maintaining electrolyte contact. The example given below (titration of Cl-) demonstrates a problem encountered with a non-isolated counter electrode. Ag. and from that point spongy black silver deposits start flowing in the solution and large and irreproducible delays of the end point are observed. The output voltage of a galvanostat. however. As good analytical practice. Limitations of the proposed counter electrodes. With a sinter separator. is considerably increased by the separator.formed at the counter electrode). H+ formed at the generating electrode is counterbalanced by OH. it is suggested to test whether the functioning of the nonisolated counter electrode meets all expectations. Several electrode materials are suitable as isolated counter electrode: Pt. Thin tubes (inner diameter ~3. The counter electrode may be kept in a single armed bridge with a fine porous membrane. while mercury being a liquid metal. The bottom end of the tube is sealed with a small soft plug (silicon rubber. The electrolytic resistance between the counter and the generating electrode. the central condition of a small-area counter is violated in the case of silver. at a generating current of 2 mA.1 Ag). Rcg. Another benefit of this approach is that it also largely decreases the possibility that the analyte or its product would react at the counter electrode. is mainly determined by the potential drop iRc-g. at ig =20 mA.the titrant at the counter electrode is rendered virtually zero on the basis of geometric and kinetic considerations. titrations at which the products formed at the counter electrode react with the analyte (in the titration of OH-with non-isolated counter electrode. Working electrodes. 2. 3. The area of the counter electrode may be smaller than that of the working electrode (Ac > 0. forms dendrites. Design and materials Isolation between the counter and generating electrodes is achieved by several ways: 1. The principles outlined above are suitable for most types of titrations. Thirsty glass tubes are the best separators in view of low resistivity and effective separation between generating and counter compartments.7. The electrolytic resistance Rc-g is easily measured by a conductometer connected to the counter and working electrodes. The difference between the two titrants is that silver. Vc-g. which may be deposited on the non-isolated counter electrode.6. Materials and shapes The choice of material for the generating electrode is made according to the electrode reaction in which the titrant is generated: . etc. For example.5 mm and wall thickness ~1 mm) are recommended for . In this case there may be some diffusion from the counter electrode compartment. Isolated counter electrodes. that due to safety considerations the galvanostats for coulometric titrations are usually constructed with limitation of the output potential. 3. Au. The product iRc-g can reach considerably large values. the product iRc-g alone reaches 10 V.can be performed with electrogenerated Ag+ or with . C. Rc-g may be as high as 500 . the silver dendrites start to protrude toward the solution and form a barely visible web with considerable area. W (tungsten only as cathode). The overall potential across the cell. typically 300 s. for coulometric titrations is limited to ~40 V. After certain incubation period. Vc-g. and thus it is advisable to complete the titration quickly. The electrodes are placed in separate vessels joined by an electrolyte bridge. isolating it from the solution being titrated. It should be noted. does not. In place of a porous membrane. adsorbent glass with 28% of volume void and 4 m average pore diameter. Thus. viton or others).

The problem is the fast disintegration of the gold. The stronger the oxidant. (IV) Pt UO2SO4 Ag Ag Hg(Ag) Hg EDTA Hg(Ag) Hg-EDTA2- OH- Pt H2O + Pt H2O Precipitation Ag(I) andcomplexation agents Hg(I) Acids and bases Generating electrode H Inert electrodes. Several examples will be given. Mercury pool electrodes are commonly mentioned in the literature. silver may be used as rods (2 or 3 mm diameter) or foils. Cl2) poses a problem due to competing reactions.Typical Electrogenerated Titrants Electrogenerated titrant Oxidants Reductants Reagent precursor Br2 Pt Br- I2 Pt I- Cl2 Pt Cl- Fe(II) Pt Fe(III) Cu(I) Pt Cu(II) Sn(II) Au Sn(IV) U(V). If this limit is exceeded. Wide-looped spirals are effective in uniform distribution of the titrant. For very strong oxidants the electrode surface of even noble metals becomes covered with oxides: and at more positive potentials oxygen is evolved due to electrooxidation of water: High current efficiency is achieved by: . the higher the potential of the generating electrode during the electrogeneration of the oxidant. Most instruments designed for coulometric titrations operate up to 40 V. While in a large group of titrations any inert electrolyte can be used. (ii) decreasing the resistance of the diaphragm separating the counter electrode compartment or (iii) decreasing the current. but unless special precautions are taken. The electrogeneration of strong oxidants (Ce(IV). mainly Pt or Au. the following measures can be taken: (i) increasing the concentration of the supporting electrolyte. they are unsafe. which can be used over years. The shape of the electrode is dictated by the price of the metal. 3. all other electrodes are convenient and safe for use. Electrogenerated Ce(IV).8. Except for mercury. We recommend the use of mercury-coated silver electrodes. Mercurycoated gold electrodes have been proposed as substitute. are used in redox reactions involving soluble species. Platinum and gold are used as thin-foiled flags or thin-wired spirals. Supporting electrolyte The prime task of the supporting electrolyte is to reduce the resistance between the generating and counter electrodes so that the voltage between them is within the dynamic range of the galvanostat. Because of its relatively low price. there are several cases in which both the type and the concentration of electrolyte play a role in the chemistry of the system. Active electrode as Ag and Hg are used for the generation of Ag(I) and Hg(I). Dense-looped spirals in the contrary can impede uniformity.

70 The respective current efficiencies are shown in the right figure. shifting the potential of the reaction of interest to more negative potentials by (i) increasing the concentration of the precursor: for a given current density. the higher the concentration of the precursor.44 1. and below the lower limit a formation of platinum oxide interferes.shifting the water decomposition to more positive potentials by increasing the proton concentration. (ii) addition of complexant that stabilizes the titrant in respect to its precursor. The current-potential curves for oxidation of Ce(III) in different acid solutions are given in the left figure. . In H2SO4 the negative potential shift results from the complexation of Ce(IV) with . The main difference between the two acids is in the negative shift of the potential for the generation of Ce(IV). Current efficiency for electrogeneration of Ce4+ as a function of current density and solution composition. and c) the current density is limited to 1 . The values of are given in the table below: Acid 1 M H2SO4 1 M HClO4 vs NH E. Optimal conditions for generation of Ce(IV): · Presence of 2-3 M H2SO4 · Precursor 0. is high. close to its solubility limit. Beyond the upper limit there will be a competition from the oxidation of water. The effect of the acids on the background currents is elatively small.8% is achieved under the following conditions: a) sulfuric acid (3 M) rather than perchloric acid is used because of the complexation ability of the former with ceric ion. b) the concentration of the precursor. The plots for the background due to oxide formation and oxygen evolution are also included. A current efficiency of 99. Ce(III). the more negative the potential of its electrooxidation. V 1.2 M Ce(III) · Current density 1-10 mA/cm2 A relatively narrow range of optimal current density characterizes the electrogeneration of strong oxidants. Current-potential plots for oxidation of Ce3+ and the respective plots for the oxidation of water at a Pt electrode.10 mA/cm2. The electrogeneration of Ce(IV) was thoroughly studied by Lingane1 (see figures below).

with electrogenerated Hg22+. (c) with a non-isolated counter electrode at which only inactive products are formed. However. the potentiometric indication obtained with dual polarized electrodes is better defined with HClO4. 3. Br. (b) with a non-isolated small-area counter electrode. Cells A great variety of cells and electrode arrangements are found in the literature. The minimal concentration is 30 mM. in spite of the fact that the Ksp of AgI is about four orders of magnitudes lower than that of AgBr. While both HNO3 and HClO4 are effective. The cell recommended here with different generating electrodes is shown in Fig. Volumes in the range of 0. in excess of halide. section 3. Collecting data Coulometric titrations take little time and you are advised to repeat each one at least five times and carry out a statistical analysis on the results. Titration of Cl. In the concentration range of interest.5.9. Such an electrode is described in this chapter. standard deviation and reject data according to rules and common sense. designed to hamper direct reaction of the titrant at it.is the most suitable halide (Fig. In order to keep the concentration of the soluble silver species lower than 10-6 M. 3. Beyond 50 mM no increase in the rate is observed.3 . the concentration of Br. The presence of strong acid is essential for the precipitation reaction to proceed in reasonable rate. SUMMARY OF COULOMETRIC TITRATIONS .Non-isolated Ag anode in a solution of halides (counter electrode in titration of H+). Fig.1 to 200 ml are used.3-7. soluble complexes are formed. 5-100 mM. For each experiment report mean.5). The working volume in the lower part of the cell is 3 to 10 ml. The role of the halide is the formation of an insoluble silver salt.should not exceed 50 mM. The role of the acid is not understood.3-7 Cells and electrodes in coulometric titrations: (a) with an isolated counter electrode. The least suitable is I-.10.

is in the form of I-3 ) .1 M KI and 0. Electrode reactions: anode: (I2 in excess of I. 4. 3.Exp.Twin platinum electrodes. 5. Titration of As(III) Chemicals 1.Non-isolated platinum. 2.5 mM As2O3 solution Combined 0. indicating .5 M H2SO4 (for pretreatment of Pt electrodes) Electrodes: generating . counter .1.Platinum. carbon or tungsten (area 0. 5 mM As2O3 solution 0.03 .0.1 cm2).1 M NaHCO3 solution 1% starch solution (freshly prepared) 0.

chemical standards and others. The clock should be zeroed at the beginning of each titration. . but to avoiddisproportionation of iodine the pH must be smaller than 9.500 ml of the 0. In this part of the experiment you will repeat the above titration. You observed the generation of the titrant (I2 formation) and determined the end point with reasonable accuracy and relative ease.cathode: (before the end point) (after the end point) The titration of As(III) is based on the reaction: The optimal pH range for performing the reaction is 7 . using the repetitive mode of titrations (Titrimetric Methods of Analysis. Pipet 0. This color will be taken as the end point of the titration. Complete oxidation of As(III) requires pH above 7. Return the timer to zero. Start the stirrer.5 mM arsenite solution.5). use of clean glassware. Adjust the current to 20 mA. Set the timer back to zero. Repeat until at least three consecutive values agree to within ± 0. Then operate the current on-off switch intermittently until a light blue color develops in the entire solution. analytical balances. burettes.500 ml of the sample into the vessel and repeat the coulometric titration. Note that the auxiliary electrode is not isolated. Since the titration is performed in a continuous mode. At this stage the current should be stopped for short periods of time (~0.NaHCO3 solution to cover the electrodes. Dilute your unknown arsenite sample in the volumetric flask to the mark and titrate 0. well-defined end point is observed without passing current between the twin indicating electrodes (note.500 ml of the 5 mM arsenite solution into the vessel and titrate with rapid stirring until the same light blue color develops. Pretitration. (ii) The end point is determined potentiometrically using two identical platinum electrodes. Turn on the current for a short time (~1 s) and note the darkening of the solution. Several runs may be made in the same solution. Why I2 is not reduced at the cathode prior to the end point? Add to the titration vessel just enough KI-NaHCO3 solution to cover the electrodes and 2 drops of 1% starch solution.500 ml portions of it as you did before. b) Potentiometric determination of the end point In the above experiment you performed your first coulometric titration. its standardization and storage. Two improvements are introduced in this section: (i) The titration is performed with monotonic generation of titrant. Pipet 0. The bicarbonate used in this experiment has the ability to restrict the pH in this range (Explain! Hint: cf. What accuracy would you expect to obtain in this case using the visual end-point determination? Try to envisage what effort would be required to perform the same titration in its volumetric version: preparation of titrant solution. but with an arsenite solution ten times more diluted. Note: Disproportionation of I2 at pH > 9: Procedure a) Visual detection of the end point Insert the electrodes into the cell and connect them to the coulometer. and for the indicating electrodes at 0. section 1. pipet another 0. pipettes. Set the current for the generating electrodes at 2 mA. that for point-by-point titration a small constant current (~1 A/cm2) should be passed between the indicating electrodes). Repetitive-monotonic titration.5 A. Add to the titration vessel just enough KI . As the end point is approached. Exp. the titration should be stopped periodically to allow the iodine (seen as blue streaks emanating from the generating electrode) to react before addition of the next portion of the titrant.9. then stop the titration and record the time. 3 in Potentiometric Titrations). Insert the indicating twin platinum electrodes.1 s).2 s. Add a small amount of the arsenite stock solution dropwise until the color disappears.

Now reverse the polarity once again and titrate. . Let the titration continue until the same color is reached. Compare the average with the time of the first titration. Compare the two types of titrations and comment. but without passing current between the indicating electrodes.2 seconds agreement between the results. Perform an additional series of titrations under the above conditions.500 ml portion of the sample and continue to titrate. 3. Pipet 1.2.0 mM HCl 0. Electrode reactions cathode: anode: Pretitration.Silver (~1. You should strive to reach a ±0. Check that the counter-electrode compartment is filled with electrolyte (1 M KNO3).5 mm wire). Add 1. The bromide deposit should be mechanically removed from time to time. Acid-base titrations 0. This procedure. Perform a pretitration at a current of 10 mA as explained above in Procedure (a).05 M KBr to cover the electrodes and 2 drops of the indicator solution. Several runs may be made in the same solution. tungsten (only as cathode) or carbon.= AgBr + e Acids can be titrated with a non-isolated silver counter electrode in presence of KBr as background electrolyte. Titrate at a current of 10 mA until a color change is observed.1 M KNO3to cover the electrodes. Add just enough of 0.0 mMHCl and titrate. counter (isolated) . add to the cell an additional 0. A sample can also be pretitrated by simply reversing the polarity of the electrodes and passing the same current for the same length of time. Several runs may be carried out in the same solution. b) in the unknown. Chemicals 1. Stop the titration somewhere after the end point. 2. In this case the anodic reaction is the formation of AgBr.Titrate until the expected potential peak is observed.05 M KBr 5.00 ml of 5. Measure the distances between the end points and calculate the average time and the standard deviation.3 cm2 area). The time elapsed from peak to peak is the time corresponding to the end point and does not include the time lag of the electrodes. Replace the isolated platinum electrode with a silver electrode. Set the timer back to zero. 2 drops of the indicator solution and enough of 0. as received in the volumetric flask. Add to the coulometric cell few drops of 5. This change of color will be taken as the end point of the titration. Insert the generating electrodes into the solution.1 M KNO3 0. Electrode reactions cathode: anode: Ag + Br. Exp. Perform a series of repetitive titrations in the same solution.Platinum. Report the concentration of As(III) in mol/l: a) in the stock solutions (note that the stock solutions are not standardized).Platinum. Procedure (b) Electrodes: generating . which adheres to the electrode and there is no need to isolate the counter electrode. however.Platinum (~0. 4.1% Bromothymol Blue or Methyl Red solution Procedure (a) Electrodes: generating . counter (non-isolated) .0 mM HCl.00 ml of 5.0 mM HCl into the vessel. brings to a progressive dilution of the analyte and the experiment should be started anew after several runs. The composition of the solution is now the same as it was before the start of the first titration.

5).5 A. . 4. Why is it necessary to separate the electrode in one case and not in the other? 3.over titration with a solution of NaOH? 7. the possible formation of small amounts of Hg does not affect the accuracy of the titration. 5. Procedure The titration is performed in the repetitive-monotonic mode (Titrimetric  Methods of Analysis. Determination of chlorides in drinking water with coulometrically generated mercurous ion Chemicals 1. Methanol 2. What are the reactions at the counter electrode? 2.Przybylowicz and L. 8. Cathode: At low concentration of chlorides (lower than 10 mM). What is the advantage of coulometric generation of OH. Is it possible in this case to use platinum and silver as the generating electrode pair? 6. 100 ml of 0. Electrode reactions: Anode: The mercurous ion () is the main product.B. describe the reactions taking place at the working electrodes. Could the generating and counter electrodes be replaced by graphite instead of platinum? Explain. 2+ Fig. 28. Is a reagent precursor necessary in acid-base reactions? Explain. section 1. Why is it not convenient to titrate coulometrically large volumes of more concentrated solutions (e.Twin mercury-coated silver electrodes. 799 (1956)).Mercury-coated silver electrode. 1.Chem.g.2 M HClO4 Electrodes: generating . Suggest a coulometric apparatus for the titration of a) dichromate. the argentometric titration is not practical because of the relatively highKsp of AgCl (1.1 M HCl)? Exp. However. since in both cases one electron per one chloride anion is involved. at various stages of the titration. With the help of current-voltage curves.Non-isolated platinum or tungsten electrode (area ~0.Report the normality of the acid as obtained by the two sets of electrodes. Anal. 5 mM HCl or/and drinking water samples 3. Set the current for generating Hg(I) to 2 mA and the current for the indicating electrodes to 0. Questions 1.05 cm2). The solubility of Hg2Cl2 is several orders of magnitude lower in 70-80% methyl alcohol (Fig.3-8) and mercury ions can be generated at 100% efficiency from a mercury-coated silver anode. The end point is determined potentiometrically with two identical mercury-coated silver electrodes at constant current of 0. Rogers.P.6·10-10). Describe an experimental method for a base titration. 1. counter .5 A (~2 A/cm2).. b) bromide.3-8 Apparent solubility product (left axis) and solubility (right axis) of Hg2X2 as function of percentage of methanol (data taken from E.. indicating . 3.

0 mM KBr or KI solution. ~4 ml 0.2. Observe the titration curve. where steady-state potentials are reached extremely slowly. 2. Measure the distances between the peaks and calculate the average time and the standard deviation.2 ml (5 drops) of 1. Exp. 4. . Amperometric indication of the end point Principle of the method. 5. Start to titrate. Add an additional 0. Concentrations of Fe2+ as low as 20 M can be determined in continuous titrations with a precision of 2%. Is the addition of a precursor necessary in such a case? 3.or I.in ppm and in mol/l. Add to the coulometric cell a 0. which take place at the silver generating electrode at various stages of the titration. 3. Compare the average with the time of the first titration. Note: PVA is a surfactant. Use the repetitive-monotonic method as described in Titrimetric Methods of Analysis. Clean the silver wire with a fine grade emery paper and rinse it with distilled water.Silver and platinum electrodes.500 ml of 5. At the end of the experiment clean the electrode and store it in the vessel provided. It hampers the coating of the generating anode with AgX. The time elapsed from peak to peak is the time corresponding to the end point and does not include the time lag of the electrodes.3% PVA solution.1 M KNO3 5. In order to avoid the formation of oxides we propose an amperometric type of indication. 5. indicating . With the help of current-voltage diagrams list the reactions.Twin silver wires. In the titrations carried out in this experiment the electrode itself took part in the reaction.2 M HClO4 and one drop of 0.1 M KNO3. Report the concentration of the halide in mol/l. Make several more additions of the sample. Continue to titrate. Electrodes: generating . about 0. Continue the titration until the expected potential peak is observed.500 ml sample of tap water or chloride solution. The response of the electrode becomes sluggish at low concentrations and is totally unsuitable for automatic titrations. Carry out a titration at a generating current of 2 mA.2 M HClO4 and just enough methanol to cover the electrodes. The reason for the failure of potentiometric indication is the formation of oxide on the platinum indicating electrode as the equivalence point is approached. 0. 4.with generation of Ag+ 0.0 mM KBr or KI 1. 4. Is this type of automatic titration possible in the case of an acid-base titration with a glass electrode? Why? Exp.5. Titration of Br.2 M HClO4 0. Stop the process at any point after the peak of the end point. What is the purpose of the KNO3? 5. where the indicating electrode is kept at a constant potential. section 1. Why the counter electrode may not be isolated? 4.3% PVA (Polyvinyl alcohol) Chemicals 1. Procedure Add to the coulometric cell 0.2 ml (5 drops) of 1. negative to the potential at which oxides are formed5. The silver generating electrode gradually acquires a coating of silver halide. The potentiometric indication for the titration of Fe2+ with Ce4+ is not applicable at low concentration levels (< 5 mM). Questions 1. 2. Titration of Fe2+ with coulometrically generated Ce4+. Report the concentration of Cl. 3.500 ml portion of the sample to the previously titrated solution. which isolates electrically the electrode and should be removed mechanically from time to time.

1 M Ce(NO3)3 in 3 M H2SO4 2. In order to avoid the oxidation of Fe2+.Fig. C. (b) Voltammograms at different stages of the titration (progress of titration F = 0 – 1. Determination of ascorbic acid in a Vitamin C tablets The titration is based on the following reaction: Ascorbic acid + Br2 + H2O = Dehydroascorbic acid + 2Br.3-9 (a) Repetitive coulometric titration of 1 mM Fe2+ with electrogenerated Ce4+. Calculate the concentration of Fe2+ in the solution. Use the repetitive mode to perform a series of titrations.2 cm2 area) vs Ag/AgCl/1 M KCl reference electrode (E = 420 mV).05 Indicating . is recorded. the time of the interruption between subsequent titrations is to be kept short (not more then few seconds).Platinum wire (area ~0. 3 M H2SO4. With the help of current-voltage diagrams. 4 ml 0. 3.16 cm2 area).3cm ) and non-isolated Au counter. Treatment of results 1. W or Au. 0. 2.2 cm2) and reference electrode.78 mM Fe2+. Titrate with a generating current of 2 mA.500 ml of 2 mM Fe2+ solution. list the reactions that take place at the working generating electrode at various stages of the titration.1 M Ce3+ solution and 0. which affects the electrode processes. Rotation rate: 400 rpm. Generating electrodes: Pt 2 (~0. It is adviced to add the new portion of analyte without interrupting the titration. Initial composition: 200 L 1.Platinum anode (area 0. Generating . keep the cell closed. Initial composition: 1 mM Fe2+ in 0. ~0. A constant potential of +420 mV vs Ag/AgCl/1 M KCl is applied to the indicating electrodes. Electrode reactions anode: cathode: Overall reaction during titration: Procedure The progress of the titration is followed by amperometric indication. 2 mM Fe(NH4)2(SO4)2 in 3 M H2SO4 Electrodes: cm2). 6.+ 2H+ .2 . Chemicals 1. The current. Add to the coulometric cell about 4 ml of 0. Amperometric indication: Pt electrode (0. ig = 1. To avoid penetration of oxygen.1 M Ce(NO3)3 in 3 M H2SO4.1 cm2) and non-isolated cathode (Pt. What is the role of Ce3+? Exp. flowing in the indicating system.1 M Ce(NO3)3.0 mA.4) of Fe2+ at a PtRDE (0. (The optimum current density range is from 1 to 10 mA/cm2).

500 ml of the Vitamin C solution to the coulometric cell.Isolated platinum wire or graphite in 0. You are provided with a Vitamin C powder. Report % of ascorbic acid in the tablet. obtained from about 10 Vitamin C tablets.Platinum.2 .05 M KBr compartment solution. add about 5 ml of 0. Use the repetitive mode of titration.05 M KBr Electrodes: generating . indicating .05 M KBr and titrate at a current of 2mA.3 cm2). Note: Keep the Vitamin C solution out of light and perform the titration within two hours after the preparation of the solution.0. Vitamin C tablets 2. make up to volume. .Twin gold electrodes (area 0. The resulting solution is somewhat cloudy due to the presence of inert substance in the tablets. Dissolve in water 50 mg of the powder in a 250 ml measuring flask. 0. counter . Procedure The bromine is coulometrically generated at a platinum electrode and the end point of the titration is followed potentiometricallyby passing a small current of about 0. Transfer 0.5 A between the indicating electrodes.Chemicals 1.