Coulometry and Conductometry

Coulometry and Conductometry
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CHAPTER 9
METHODS BASED ON FARADAY'S LAWS There are two important electroanalytical methods based on Faraday's two laws of electricity which were suggested in the first half of the nineteenth century. These two methods are electrogravimetry (or electrodeposition) and coulometry. The first Faraday's law states that the amount of a substance that is generated at an electrode in an electrochemicalcell is proportional to the amount of electricity which passes through the solution in the cell. This is simply a direct relationship between the amount of electricity passed and the amount of substance liberated at the electrode. When two species, for example, are present in solution Faraday's second law suggests that the amounts of each that are either deposited or liberated by the same quantity of electricity are proportional to their chemical equivalents. This means that if enough electricity was passed to deposit 107.8 g of Ag this amount of electricity is capable of depositing 63.5/2 g of Cu or 55.8/2 g of Fe from Fe2+ solution or 65.4/2 g Zn, ...etc. If all previous species are present in solution, this amount of electricity will result in the deposition of chemical equivalent ratios of these species. Note that the chemical equivalent of a cation is simply the atomic weight of the element divided by the charge of the cation. ELECTROGRAVIMETRY Usually, a metal or metal oxide deposit is formed on the cathode surface when controlled current or potential is applied properly. The nature of the deposit may range from coarse to fine crystalline or porous particles depending on the conditions used. Low current densities usually result in good fine deposits that adhere well to the electrode surface while porous deposits are obtained at high current densities because of high rate of hydrogen evolution, at the electrode, at the same time of metal deposition. It is therefore necessary to keep the rate of metal deposition as small as time permits and to use conditions which satisfy this trend. However, reduced metal diffusion to electrode surface will result in high resistance to ion transfer due to ion depletion from the electrode surface. In such situations stirring the solution may be necessary. This is sometimes called accelerated electrolysis. Constant Current Electrogravimetry When the sample to be analyzed contains one species which can be electrodeposited, electrogravimetry is conducted at constant applied current. The end point can be detected using visual indicators or some other electrochemical methods. If other species are present in the sample, they may be codeposited with the analyte since potential of the cathode assumes more negative values as the electrolysis continues which may agree with the electrodeposition potentials of these species. Constant Potential Electrogravimetry The presence of more than one species that can be deposited in an electrolysis experiment limits the use of constant current electrogravimetry. Instead, constant
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potential that is enough to deposit the first species is applied. When all the amount of that species is deposited, the potential is adjusted so as to deposit the second one. This procedure continues till all species are determined. It should be clear that reduction potentials of each species should be sufficiently different from the other species in order to successfully analyze the sample. This technique can also be regarded as a separation technique where species can be selectively deposited or left free in solution depending on the system in question. A very important advantage of electrogravimetric methods is that a 100% current efficiency is not required since only the weight of the deposited species is important. Standard solutions are also not required. COULOMETRIC METHODS As the name implies, the quantity of electricity passed through the cell is measured and is then related to analyte concentration. In this respect, it is necessary to define the Faraday which is the quantity of electricity that generates one equivalent of an analyte. One Faraday (F) is equal to 96,487 coulomb (c) and the number of coulombs (Q) can be defined as Q = it (1) where i is the current intensity in amperes (A) and t stands for the time in seconds (s). Two main coulometric procedures are used. The first involves holding the potential of the working electrode constant throughout electrolysis. This is referred to as constant potential coulometry. The second involves maintaining a constant current followed by calculation of the amount of electricity required from equation1. This procedure is referred to as coulometric titrations. Regardless of the type of procedure used in coulometry, the current efficiency has to be 100% because this current will, indirectly, be related to analyte concentration. Coulometric Titrations Coulometric titrations are very important in analytical chemistry because reliable measurements of analytes can take place without the need for careful preparation of standard solutions. Current is easily measured rather than volumes or weights. Also, reliable accuracy and sensitivity are routinely obtainable. An additional extremely important advantage of coulometric methods involves the possibility of using unstable titrants which are impossible to use in conventional volumetric methods. This is because these titrants are generated in situ and are used as soon as they are formed. The end point can be detected using visual indicators or some electrochemical methods like potentiometry or biamperometry. In all cases, fast reaction between titrants and analytes are required. Instrumentation involved in coulometric titrations are very simple and can be conveniently assembled from basic components. A constant current source and a method for accurate current measurement are essential. Applications of Coulometric Titrations Coulometric titrations had been used for a wide variety of applications.
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Neutralization of weak as well as strong acids can be conveniently achieved using electrochemically generated hydroxide ions. On the other hand, bases can be neutralized using anodically generated H3O+. The same concept can be applied in case of precipitation reactions where electrogenerated Ag+ ions react with halides resulting in precipitation of the silver halide. electrogenerated oxidants can be conveniently used in redox titrations. Cl2, Br2 and I2 are electrogenerated and used for the oxidation of many reducing agents. Again, the exclusion of the necessity for standard solutions, the high accuracy, the less reagents required, and the speed of analysis give coulometric titrations their widespread use and special importance.
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Applications
Experiment 20: Coulometric Determination of Arsenic by Electrogenerated Bromine and Dead Stop End Point Detection Background Coulometric titrations are widely used for determination of many important analytes. In situ generation of titrants which are, otherwise, unstable is an important feature of the method. In this experiment, arsenic is determined by electrogenerated bromine and the end point is detected through the use of an auxiliary dead stop end point detection circuit. The cell is, therefore, composed of four electrodes. Two small and identical platinum electrodes for end point detection, one large platinum electrode called the generator electrode and an isolated auxiliary electrode which is the cathode (in this experiment). The indicator electrodes of the detection circuit pass current only when Br2 and Br- are present in excess. Reactions a. At Generator Electrode 2 Br- = Br2 + 2 e b. At Auxiliary Electrode 2 H+ + 2 e = H2 or, 2 H2O + 2 e = H2 + 2 OHc. Redox Reaction H2AsO3- + Br2 + H2O = AsO4- + 2 Br- + 2 H+ Chemicals and Reagents a. Provided 1. Solid KBr. 2. 5 M NaOH solution. 3. Arsenic unknown (predried and desiccated). 4. 5 M HCl solution. 5. Predried and desiccated arsenic trioxide (analytical grade). b. Need Preparation 1. Arsenic solutions as described in steps 1 and 2 of the procedure. Apparatus
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Coulometric titrator, or components necessary for the construction of the circuit shown in the figure below.
Procedure 1. Dissolve an accurately weighed sample of analytical grade arsenic trioxide (0.08 -0.1g) into a 500 mL volumetric flask. This can be achieved by dropwise addition of 5 M NaOH solution and swirling. When the sample is dissolved, add about 200 mL of distilled water followed by 5 M HCl equivalent to the amount of the 5 M NaOH added. Adjust the final HCl concentration in the flask to 0.2 M HCl. 2. Repeat for the unknown arsenic sample but take about 0.1 to 0.15 g of the unknown (accurately weighed). 3. Dissolve about 6 g of KBr in about 100 mL of distilled water in a 250 mL beaker into which a stirring bar was dropped. 4. Set up the circuit described in the attached figure and adjust the location of the electrodes. The two small platinum electrodes are connected to the detection circuit while the other large platinum electrode is the generator electrode. 5. Start the stirrer at a suitable rate which should be constant throughout the experiment. 6. Electrolyze for few seconds by closing the generator circuit through the switch. The galvanometer should read a current of about 5 mA. This is a necessary step for the oxidation of available oxidizable species. Switch off the generator circuit. 7. When the indicator galvanometer deflects, add dilute arsenite solution dropwise to consume any bromine in solution. 8. Transfer 10 mL of the standard arsenic solution and switch on the generator circuit and record the time versus indicator galvanometer reading. 9. Repeat steps 7 and 8 three times for the standard and three more times for the unknown arsenic solution.You do not have to discard the solution each run. 10. From results obtained in steps 8 and 9, plot current versus time, and find the percentage of As2O3 in the unknown sample.
Figure: A set up for coulometric titrations.
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CHAPTER 10
CONDUCTOMETRIC METHODS Solutions that contain ionic species conduct electricity. Positive and negative ions migrate in certain speeds towards electrodes of opposite charges. The conductance is a function in the rate of movement of these ions or the mobilities of both ions, the number of ions present, and the charge on each ion. Conductance can be defined as the reciprocal of resistance which means that the conductance of an electrolytic solution is simply the reciprocal of its electrical resistance. Usually, conductance is given the symbol G and given the units of ohm-1 or, in SI units, the siemens (S). The ability of a solute to conduct electricity is called molar conductance which is defined in the equation: K L = ____ C
(1)
Where L is the molar conductance of 1mde of the solute present in a cell the electrodes of which are 1 cm apart, C is the concentration in moles per L and K is the specific conductance which is defined from the relation: A G = K ____ L
(2)
Where A and L are the cross section area of the electrodes and the spacing between them, respectively. The specific conductance is constant for a specific cell configuration and is measured in order to substitute in equation 1 so as to calculate the molar conductance. Molar Conductance at Infinite Dilution The infinite dilution concept is the situation where the concentration of a solute becomes infinitely small and the molar conductance is independent on concentration. Two opposing forces act on an ion present in a conductance cell, the electrical force and the frictional force. Electrical forces tend to force the movement of an ion to the oppositely charged electrode while this is partially hindered by the frictional forces exerted by the solvent molecules which retard ionic mobilities. Two other forces are especially important at finite solute concentrations. The first is the electrophoretic force which results from the retardation of the ionic atmosphere by the viscosity of the solvent. The second force is a relaxation force where charged ions surround each ion of opposite charge. When an electric force is applied, the
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central ion tends to leave the ionic atmosphere and move towards the oppositely charged electrode. At the same time, the counter ions tend to either migrate to the other electrode or to move with the central ion. This results in the distortion of the ionic sphere which is said to relax. Molar Ionic Conductance The molar conductance of a solute can be broken into two components: L=l++l(3)
Where l + and l - are the molar ionic conductance of the positive ions and negative ions,respectively. Since the conductance is dependent on concentration, equivalent ionic conductance of the different ions is reported at infinite dilution. An equivalent ionic conductance of an ion is defined as its molar conductance divided by the charge on the ion (positive or negative). Conductometric Titrations The most important uses of conductance in analytical chemistry are related to conductometric titrations which exhibit excellent features. Instrumentation required are simple where a low cost conductance apparatus is adequate. Titration of weak acids and bases that are otherwise impossible to titrate or acid-base system for which no suitable indicators are available are well suited to conductometric titrations. Conductance will be minimal at the equivalence point while high values before and after titrations or at either extreme allow easy location of the equivalence point. Another example of the importance of conductometric titrations are the precipitation and complexometric titrations. Since the conductance of a sparingly soluble compound is minimal, the equivalence point can be easily located. This is significantly important for precipitation titrations of some systems that have no suitable indicators, or complex forming reactions. Conductometric titrations can also be used for mixture analysis where a separate end point is obtained for each component.
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Applications
Experiment 21: Conductometric Titration of a Mixture of Acetic and Hydrochloric Acids Background Strong acids, like HCl, are completely dissociated in water and their conductance decreases as neutralization proceeds. This is because hydronium ions have greater mobilities in solution. However, weak acids show an increase in conductance when titrated with NaOH due to release of ions of greater mobilities. Therefore, titration of a mixture of HCl and acetic acid should be possible by measurement of the relative conductance in the course of the titration. Reactions HCl + NaOH = H2O + NaCl CH3COOH + NaOH = CH3COONa + H2O
Chemicals and Reagents a. Provided 1. NaOH solution, approximately 2 M. 2. Predried and dessiccated potassium hydrogenphtalate (KHP). 3. Unknown mixture of HCl and CH3COOH. 4. Phenolphthalein indicator. 5. HCl solution, approximately 2 M. b. Need Preparation 1. 500 mL of standard NaOH that is about 0.1 M. Dilute the stock NaOH solution provided and standardize against KHP. Method: Transfer approximately 0.6 g of the predried and desiccated KHP (accurate weight) into a 250 mL conical flask, dissolve in about 50 mL of distilled water and titrate against dilute NaOH solution to the phenolphthalein end point. 2. 250 mL of 0.1 M HCl solution. Dilute the stock HCl provided and titrate against standardized NaOH to the phenolphthalein end point. Apparatus and Materials 1. Electrical conductivity meter. 2. Magnetic stirrer. 3. stirring bar.
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Procedure 1. Transfer, accurately, 25 mL of the mixture into a 250 mL beaker and dilute to about 100 mL using doubly distilled water. 2. Drop a stirring bar into the beaker and insert the conductivity cell into the solution. 3. Start the magnetic stirrer and adjust the rate at a suitable speed. Record the conductance value. 4. Start addition of the NaOH titrant and record the conductance value after each addition of 0.5 mL increments till about 30 mL of the base are added. 5. Repeat steps 1 through 4 and record your results. 6. To a fresh 25 mL of the mixture add 40 mL of standard NaOH (accurate) and dilute to about 100 mL using doubly distilled water. Drop the stirring bar, insert the conductivity cell, and start the magnetic stirrer at a suitable rate. Record the conductance value. 7. Titrate against standard HCl and record the conductance value after each addition of 1 mL increments of the acid. 8. Repeat steps 6 and 7 and record your results. 9. Plot graphs of results obtained from the direct and indirect titrations, and find the concentration of HCl and CH3COOH in the original mixture. 10. Report your results as g acid/100 mL.
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Experiment 22 : Precipitation Titration of Barium with Conductometric Detection Background Barium ions may be precipitated as barium sulfate and the titration can be followed using conductance measurements. Conductivity can be of significant importance for following a titration for which no suitable indicator exists. This can, primarily, expand the scope of precipitation titrations and validate these methods to a broader range of potential applications. Reactions BaCl2 + Na2SO4 = BaSO4 (s) + 2 NaCl Chemicals and Reagents a. Provided 1. Unknown Ba2+ solution. 2. Predried ans desiccated Na2SO4. b. Need Preparation 1. 250 mL of 0.2 M Na2SO4 standard solution. Apparatus and Materials 1. Conductivity meter. 2. Magnetic stirrer. 3. Stirring bar. Procedure 1. Transfer 20 mL of the unknown barium solution into a 250 mL beaker. Dilute to about 100 mL using doubly distilled water, drop the stirring bar, and insert the conductivity cell into the solution. 2. Start the magnetic stirrer at an appropriate speed and record the initial conductance value. 3. Titrate the barium solution with standard Na2SO4 and record the conductance reading after each addition of 1 mL increments. 4. Repeat steps 1 through 3 and plot your results as conductance versus mL of Na2SO4 added. 5. From the graph, find the equivalence point and report your results as g BaCl2 / 100 mL in the original mixture.
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Coulometry and Conductometry

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Coulometry and Conductometry

http://www.monzir-pal.net/Lab Manuals/Practical Instrumental Analysis...