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Iodometric Determination of Copper

In I US O C t C i M d B f One Cent Coins Made Before and Aft 1982 d After

XX YY

Pennies are an interesting commodity. commodity They are everywhere, everywhere an always present means of currency. The penny is ingrained in our society for many different social and economic reasons.

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Penny Composition
Pennies made from 1962 to 1982 consist of 95% copper and 5% zinc. These copper rich pennies are currently worth more as a metal source than their face value. Pennies minted after 1982 to the present day are only made up of 2.5% copper. This copper is plated onto a zinc core that makes up 97.5% of the penny. The determination of copper in both pennies made before and after 1982 will be determined using the same method.

Introduction to Iodometric Determination

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Wet Chemical Analysis

M More accurate and precise th i t t d i than instrumental t l methods. Systematic errors have been detected in the past and can be accounted. More involved process Help to learn new techniques Reinforce the techniques learned so far

Process selection - Iodine

U d widely to quantitatively measure Used id l t tit ti l chemicals reactions Many analytical procedures are based on the release or uptake An analyte that is an oxidizing agent is added to excess iodide to produce iodine The iodine produced is determined by titration with sodium thiosulfate This method is called "iodometry"

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Iodometry
Ch Chosen for its straightforward procedure f it t i htf d d The reaction is rapid and quantitative The starch used is a clear and determinant indicator The reagents involved are all easily obtained and in good supply. Volumetric determination with a back titration is a well documented method of determining the amount of an ion in a solution.

Volumetric Determination
A primary standard
selected as appropriate to the ion being measured dissolved into an aqueous solution used in a titration to standardize a secondary standard solution of sodium thiosulfate

The analyte is reacted with iodide to oxidize ion to iodine The iodine is then titrated with thiosulfate with a starch indicator to determine the endpoint With the known amount of thiosulfate used to titrate the freed iodine, we can determine how much iodide reacted with our analyte and then determine how much analyte is present

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Iodometry
The iodine (triiodide) iodide redox system system, - + 2 e3 II3 The iodide ion is a strong reducing agent that many oxidizing agents can react with completely The amount of iodine liberated in the reaction between iodide ion and an oxidizing agent is a measure of the quantity of oxidizing agent originally present in the solution q The amount of standard sodium thiosulfate solution required to titrate the liberated iodine is then equivalent to the amount of oxidizing agent Iodometric methods can be used for the quantitative determination of strong oxidizing agents such as potassium dichromate, permanganate, hydrogen peroxide, oxygen, and in my case, the cupric ion.

Sodium Thiosulfate
M d f Made from dissolving sodium thi di l i di thiosulfate lf t pentahydrate salt Solution is standardized against a primary standard Iodine oxidizes thiosulfate to the tetrathionate ion: 2 I- + S4O62I2 + 2 S2O32-

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Primary Standard
I di i rarely used as a primary standard Iodine is l d i t d d for thiosulfate because it presents a problem in weighing and maintaining its solution concentration Pure copper in the form of copper wire is used as the primary standard for sodium thiosulfate when it is to be used for the determination of copper as is the case with this experiment

Secondary Standard
Upon addition of excess iodide to a solution of copper(II), a precipitate of CuI is formed along with I2. The liberated iodine is then titrated with standard sodium thiosulfate 2 Cu2+ + 5 I2 CuI(s) + I3I3- + 2 S2O323 I- + S4O62 Formation of the precipitate and the addition of excess iodide force the equilibrium to the right in a rapid quantitative reaction The net stoichiometry of the reaction is 1:1 since 2 moles of copper indirectly requires 2 moles of thiosulfate

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Indicator
The endpoint in a titration of iodine with thiosulfate is signaled by the color change of the starch indicator. The active ingredient in starch is a helical polymer of -D-gluocse called -amylose, which forms a deep blue-black complex with molecular iodine For use in this indirect method, the indicator is p y added at a point when virtually all of the iodine has been reduced to iodide ion, this helps the the disappearance of color to be rapid and sudden The starch indicator solution must be freshly prepared since it will decompose and its sensitivity is decreased

Preparation of Copper
Complex ions are ions formed by the bonding of a metal atom or ion to two or more ligands by coordinate covalent bonds A ligand is a negative ion or neutral molecule attached to the central metal ion in a complex ion In this experiment, copper and copper-clad pennies are dissolved in a concentrated aqueous solution of nitric acid, HNO3 In aqueous solution, most of the first-row transition metals form octahedral complex ions with water as their ligands: Cu(s) + 4 HNO3(aq) + 4 H2O(l) Cu(H2O)62+(aq) + 2 NO2(g) + 2 NO3-(aq) Once the pennies have been dissolved, the copper is free to react with iodide ions

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Experimental Procedure

Standardizing Thiosulfate
Measure out ~1 L of de-ionized water Heat to boiling, boil for at least five minutes Add 25 g of Na2S2O35H2O to 1-L volumetric flask, and mix with hot boiled water Add ~0.1 g of Na2CO3 as a preservative Fill to the mark and mix Transfer the solution to a 1-L plastic bottle Store in darkness when not in use to help prevent decomposition of the thiosulfate, which is catalyzed by light.

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Standardizing Thiosulfate
Three pieces of clean copper wire were weighed using about 0.20 to 0.25 g each and placed in seperate 250-mL Erlenmeyer flasks About 5 mL of 6 M nitric acid is added to each flask Dissolution is promoted by warming the solution on a hot plate De-ionized water is added to keep the volume constant. After the copper has dissolved, ~25 mL of water was added and the solution boiled for a few more minutes to remove more nitrogen oxides Add 5 mL of urea solution (1 g in 20 mL of water) with continued boiling for another minute. g g Boiling removes oxides of nitrogen which result from the following reactions: 3 Cu(NO3)2 + 2 NO + 4 H2O 3 Cu(s) + 8 HNO3 2 NO + O2 2 NO2 and the oxides are decomposed by urea: 2 HNO2 + (NH2)2CO CO2 + 2 N2 + 3 H2O

Standardizing Thiosulfate
The solution is removed from the hot plate and cooled The excess acid is neutralized with 4 M aqueous ammonia added dropwise in the hood until a blue-green precipitate of copper(II) hydroxide barely form To dissolve the precipitate and bring the solution t a pH b l ti to H beneficial t th tit ti fi i l to the titration reactions, 5 mL of glacial acetic acid was added to each flask.

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Analysis of Pennies
For the pennies, six pennies were selected, three from pre1982 minting and three from post-1982 They were cleaned with soap and water, dried, and then weighed on an analytical balance Each of the pennies are placed into a 250-mL Erlenmeyer flask To each flask, ~10 mL of 6 M nitric acid is added and the flasks were placed on a hot plate in the hood to dissolve the pennies After three hours of heating and additional 6 M nitric acid and 15.9 M nitric acid added in small amounts and de-ionized water to keep the solution level constant, the pennies were dissolved The flasks are removed from the hot plate and allowed to cool in an ice bath Then ~10 mL of 9 M sulfuric acid is slowly added to each flask by pouring down the side of the flask The solution is reheated until white fumes of sulfur trioxide appeared Throughout the heating process, red fumes of nitrogen oxides could been seen over each of the solutions

Analysis of Pennies
The flasks are then removed again and cooled in an ice bath 4 M aqueous ammonia is added dropwise right until the point where the copper hydroxide precipitate has formed To dissolve the precipitate and bring the pH to a level appropriate for the titration system, 5 mL of glacial acetic acid is added The pre-1982 penny solutions has to be diluted to get a proper amount of copper concentration that will be appropriate for the framework of the experiment The copper solution is quantitatively transferred to a 250 mL volumetric flask and diluted to the mark After dilution, 25 mL of this solution is transferred with a transfer pipet quantitatively to another 250 mL Erlenmeyer flask which is then ready for titration preparation

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Iodometric Titration
At this point, the samples were prepared and titrated one at a time. Potassium iodide is weighed and then added The flask is covered with a watch glass and allowed to stand for ~2 minutes The solution is then titrated with thiosulfate solution until the brownish color of iodine is almost gone indicated by a light tan or creamed coffee color

Iodometric Titration
Enough iodine has then been reacted to add the 5mL of starch solution And 2 g of sodium thiocyanate is added to displace any adsorbed iodine from the precipitate

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Iodometric Titration
The flask is swirled for about 15 seconds Then the titration is completed by adding thiosulfate dropwise At the end point, the bluish-gray color of the solution disappears and the precipitate appears whitish, or slightly gray

The second and third samples were treated in the same manner and titrated with thiosulfate

Data and Analysis

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Standardization of Thiosulfate Solution

Sodium thiosulfate pentahydrate FM Copper molar mass Mass of thiosulfate used (g) Volume of solution (L) Calculated Molarity of thiosulfate solution 248.18 g/mol 63.546 g/mol 25.1074 1.00 0.101 M

Standardization of Thiosulfate Solution

Trial 1 Mass of copper wire (g) M f i ( ) Mass of KI added (g) Mass of KSCN added (g) Volume of thiosulfate titrated ( ) (mL) 0.2160 0 2160 3.0024 1.9816 33.54 Trial 2 0.2438 0 2438 3.0155 2.0383 37.72 Trial 3 0.2388 0 2388 3.0012 2.0165 37.00 0.1016 M

Measured Molarity of thiosulfate 0.1013 M 0.1017 M solution

The average molarity was determined to be 0.1015 0.0002 M.

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Pre-1982 Pennies
Year of Mint Mass of penny (g) M f ( ) 1977 3.0717 3 0717 1978 3.0876 3 0876 45.85 2.958 95.82% 0.17% 0 17% 1979 3.1191 3 1191 45.59 2.963 94.31% 0.17% 0 17%

Volume of thiosulfate titrated (mL) 45.27 Measured mass of copper (g) Measured % of copper in penny 2.921 95.10%

Propagation of Error from Molarity 0 17% 0.17% Calc

The average %wt of copper in pre-1982 pennies is 95.08 0.10 with a standard deviation of 0.7530 from the three trials.

Post-1982 Pennies
Year of Mint Mass of penny (g) M f ( ) 1983 2.5147 2 5147 1985 2.5488 2 5488 9.89 0.06382 2.504% 0.005% 0 005% 1986 2.5236 2 5236 10.40 0.06711 2.659% 0.005% 0 005%

Volume of thiosulfate titrated (mL) 9.27 Measured mass of copper (g) Measured % of copper in penny 0.05981 2.379%

Propagation of Error from Molarity 0 004% 0.004% Calc

The average %wt of copper in post-1982 pennies is 2.514 0.003 with a standard deviation of 0.1405 from the three trials.

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Confidence Interval t-test

The 95% confidence interval range with two degrees of p p freedom for pre-1982 pennies was found to be
96.95 to 93.20 %wt copper The true value given at the Department of Treasury website is
(19621982) 95% copper, 5% zinc (brass)

which falls within the CI range

The 95% confidence interval range with two degrees of freedom for post-1982 pennies was found to be
2 863 to 2.165 %wt copper 2.863 2 165 The true value given at the Department of Treasury website is
(1982 present) 97.5% zinc core, 2.5% copper plating

which falls within the CI range

Sources of Error
Copper(I) iodide forms a weak complex with molecular iodine which slows down its reaction with thiosulfate.
As a consequence, once the starch indicator has turned from blue to colorless, the blue color returns after a few seconds as I2 is slowly released into the solution by the CuI[I2] complex This "after-bluing" can be avoided by adding potassium thiocyanate just before the end point is reached The thiocyanate ion, SCN-, replaces the complexed I2 from CuI[I2], releasing the I2 to solution where its reaction with thiosulfate is rapid.

Iodine may be lost by evaporation from the solution

This is minimized by having a large excess of iodide in order to keep the iodine in the tri-iodide ion state Titrations involving iodine should be made in cold solutions in order to minimize loss through evaporation.

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Sources of Error
In acidic solutions, the iodide ion can oxidize from the atmosphere
Therefore, prompt titration of the liberated iodine is necessary in order to prevent oxidation.

If the starch solution is not made fresh daily or improperly prepared, the indicator will not behave properly at the endpoint resulting in a sluggish or improper endpoint endpoint.

Sources of Error
The addition of concentrated H2SO4 and continued heating until white sulfur trioxide fumes appear will ensure that all the HNO3 has been removed
NO3- will oxidize I- and would will seriously interfere with the procedure.
The presence of the concentrated sulfuric acid aids in the exclusion of the remaining nitrogen oxides from the hot solution. The red oxides first boil off, then fumes of sulfur trioxide beginning to escape.

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Sources of Error
If excess ammonia is added, copper(II) hydroxide redissolves forming the deep blue redissolves, copper(II) ammonia complex, Cu(NH3)4 If the excess of ammonia is large, some ammonium acetate will be produced later which may keep the reaction between copper(II) and iodide ions from being complete The excess ammonia can be removed by boiling, and the precipitate will re-form

Sources of Error
Concentrated sulfuric acid has a very strong affinity for water With nitric acid itself, sulfuric acid acts as both an acid and a dehydrating agent Combined with the heating and evaporation of water in the sample, this resulted in a supersaturated aqueous ionic solution which forced some precipitates out at certain stages in the experiment Before the sulfuric acid was added to the pre-1982 penny solutions, the concentration caused copper nitrate to precipitate out After the sulfuric acid was added, it caused copper sulfate to precipitate out in well formed crystals de These two precipitates were easily redissolved by adding more deionized water and slightly mixing

Copper Sulfate Crystal

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Sources of Error
Dealing with concentrated acids and evaporation of the little amount of water in these acids can cause "bumping" or littl explosions of steam in the "b i " little l i f t i th superheated liquid Using tongs will keep hands far enough from the mouth of the flask should the solution suddenly "bump" and cause acid burns from the flung drops of concentrated acid Bumping can also cause small amounts of the analyte to fly from the flask so preventing bumping by swirling the flask, flask occasionally will ensure that none of the analyte is lost.

Elimination of Error
This experimental method has built in corrections for each of the errors mentioned previously that can occur. These systematic errors have been easily corrected by the refinement of the process The replication of the experiment is ensured b th elimination of th d by the li i ti f these systematic errors in a concise and repeatable manner

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Conclusion
Iodometric determination of copper gives a reliable measurement of copper in a sample The amount of error is low because of the correction of systematic error, and the lowered possibility of introduction of random error through the straightforward procedure The indirect titration of the iodine with thiosulfate is simple, easy to control, accurate and precise The given value of copper content of a penny fell within the measured 95% confidence interval with three trials on each type of penny With more trials, the confidence interval could be honed down to find an even more precise measured value.

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