#7.

Iodometric Determination of Copper 53

EXPERIMENT 7.

IODOMETRIC DETERMINATION OF COPPER IN BRASS

BACKGROUND

This experiment illustrates the analytical method involving the iodine-iodide

couple:

I 2 + 2e- <===========> 2 I- E° = 0.53 V (1)

This couple is important because it has a standard electrode potential that

permits the analytical use of iodine as an oxidant for substances of lower electrode
potential and iodide as a reductant for substances of higher potential. Because its
electrode potential is little affected by either pH change or complexing agents, this
couple can be used in conjunction with half-reactions that change potential with
pH or with the addition of auxiliary reagents.

Analytically useful applications include those in which solutions of iodine are

used to titrate reduced materials directly and those in which oxidizing agents are
determined through oxidation of iodide to iodine. In the latter the iodine formed is
titrated with a standard solution of sodium thiosulfate, Na2SO3.

Iodometric Determination of Copper

In this experiment the copper in a brass sample is determined by a method
involving the liberation of iodine. The sample is dissolved in nitric acid, and the
solution boiled to remove most of the nitrogen oxides formed during the metal
oxidation. The residual nitrogen oxides are eliminated by the addition of urea.
Complete removal of nitrogen oxides is necessary to prevent iodide oxidation.

Iron present in most brasses, also causes iodide oxidation. This interference is
eliminated by the addition of fluoride, which forms a stable complex with
iron(III). Next the pH is adjusted to 3.5 to 4.5, an excess of potassium iodide is
added, and the iodine formed is titrated with sodium thiosulfate.

Although the titration of iodine is the only titration of significance for which
thiosulfate is used as a standard solution, it is an important one. Other
applications of thiosulfate are few. One reason is that oxidizing agents stronger
than iodine oxidize it to a mixture of higher oxidation states of sulfur; another is
that ions of transition metals such as copper decrease the stability of sodium
thiosulfate solutions by catalytic air oxidation. Acids also make thiosulfate
54 #7. Iodometric Determination of Copper

solutions unstable by promoting disproportionation to sulfite and elemental

sulfur:

– –
HS2O3 -----------------> HSO3 + S (2)

Addition of a small amount of sodium carbonate to make the thiosulfate solution

alkaline prevents this decomposition. Water used for the preparation of standard
thiosulfate solutions may be boiled to destroy sulfur bacteria, which find these
solutions an attractive medium for growth. Alternatively, a bacterial agent such
as a mercury(II) salt or chloroform may be added.

Any of several primary standards, including iodine, potassium chromate,

potassium iodate, and electrolytic copper metal may be used to standardize
thiosulfate solutions. For this experiment copper is chosen because it is the
material being determined and is readily available in primary standard quality as
electrical wire.

The principal reactions involved in iodometric copper analysis are

(a) dissolution of sample in dilute nitric acid,

3 Cu + 8 HNO3 -----------------> 3 Cu2+ + 2NO + 4 H2O + 6 NO3- (3)

or

Cu + 4 HNO3 ----------------> Cu2+ + 2 NO2 + 2 H2O + 2 NO3- (4)

(b) removal of residual nitrogen oxides by addition of urea,

2 NO + O2 <===========> 2 NO2 (5)

2 NO2 + H2O <============> HNO2 + HNO3 (6)

and

2 HNO2 + (NH2)2CO ----------------> 2 N2 + CO2 + 3 H2O (7)

(c) neutralization of remaining acid with sodium hydroxide, followed by pH

adjustment;

(d) complexation of iron(III) with fluoride,

Fe3+ + F- <==========> [FeF]2+ (8)

 #7. Iodometric Determination of Copper 55

(e) addition of excess potassium iodide,

2 Cu2+ + 4 I- <===============> Cu2I 2 + I 2 (9)

and

(f) titration of iodine with thiosulfate,

I 2 + 2 S2O32- <===========> 2 I- + S4O62- (10)

Precautions must be taken to avoid side reactions. For instance, iodine will slowly
oxidize tetrathionate to sulfate, especially at high pH values. At low pH sulfurous
acid may be formed by thiosulfate (equation (2). Another source of error in strong
acid solution is air oxidation of iodide:

O2 + 4 H+ + 4 I- <============> 2 I2 + 2 H2O (11)

This is called oxygen error. These side reactions may be avoided by carrying out
the thiosulfate - iodine reaction in the pH range 2 - 5.

The volatility of iodine creates problems. Iodine loss can be minimized by keeping
the temperature low, titrating promptly, and adding excess iodine to stabilize the
iodine in solution as triiodide:

I 2 + I- <==========> I3- Keq = 7.1 x 102 (12)

Starch gives an intense blue color with triiodide that serves as a specific indicator.
The triiodide ion appears to be just the right size to enter the helical structure of
starch and thereby form a colored complex. The color of free iodine, red-brown in
high and yellow in low concentrations, also can be used as an indication of its
presence, but it is not so easily seen as that of the complex with starch. In acidic
solutions starch tends to undergo decomposition that is accelerated by high
concentrations of iodine. Therefore, addition of starch is best delayed until near
the equivalence point of the titration.

Most strong oxidizing agents can be determined iodometrically. An excess of

iodide is added, and iodine is produced in an amount equivalent to that of the
oxidant present in the sample. The liberated iodine is titrated with thiosulfate.
56 #7. Iodometric Determination of Copper

PROCEDURE

(Median Time 3.9 hours)

Reagent List:
Unknown Sample
Sodium thiosulfate•5H2O - prepare 0.1M soln.
Na 2CO3
HNO3 conc. 16M
copper turnings >99% pure
Urea - 4% soln. needed
sodium hydroxide pellets - 2.5M soln. needed
ammonium acid fluoride(NH4HF2)
potassium iodide
Starch - .2% soln indicator

Standardization of 0.1 M Na2 S 2 O 3 Solution

Dissolve 25 g of Na2S2O3.5H2O and 0.1g of Na2CO3 in a liter of distilled water.

N.B. This solution may be saved for Experiment 8.

Weigh accurately 0.2 g samples of clean copper turnings into 200 mL conical
flasks.1 Add 10 mL of 6 M HNO 3 to each in a fume hood. When dissolution is
complete, boil the solution for a short time to remove most of the nitrogen oxides.
Add 10 mL of water and 5 mL of 4 % urea solution, and boil again for about one
minute. Allow the solution to cool. When ready to titrate, add 30 mL of water and
then add 2.5 M NaOH until a slight permanent precipitate of Cu(OH)2 is obtained.
This will require about 15 to 20 mL of NaOH, depending on the amount of HNO3
present. Add 1 to 2 g of ammonium acid fluoride, NH4HF2, and swirl until
dissolved.

Cool, add approx. 3 g of KI, and titrate immediately to near the end point with
Na 2S2O3. When the solution has become pale yellow or buff, add about 5 mL of
fresh starch solution and titrate to the first complete disappearance of blue.2

PROCEDURE FOR THE SAMPLE

Do not dry the unknown. Determine the total weight of the unknown. Transfer
the unknown to a 250 mL volumetric flask. Dissolve the unknown with 10 mL of 6
M HNO3. Dilute to 250 mL. Pipet 25 mL into a 250 mL erlenmeyer. Add urea and
boil as described for the standards. When ready to titrate, neutralize with sodium
hydroxide and dilute to 50 mL with water. Add about 1 g of ammonium acid
 #7. Iodometric Determination of Copper 57

fluoride and swirl until dissolved. Add approx. 3g of KI and complete the
determination as in the standardization.

Calculate the molarity of the Na 2S2O3 solution. One mole of copper requires 1
mole of thiosulfate for titration. Calculate and report the percentage of copper in
the sample.

NOTES
1. Trace impurities markedly increase the resistance of copper wire. For
electrical use they are removed by electrolytic refining to a level well below a
part per thousand. Copper produced for electrical wiring is therefore an
excellent primary standard. The thin coat of oxide sometimes present on the
wire can be removed by polishing with fine emery cloth, followed by wiping
with clean toweling.

2. To avoid etching of flasks by HF, empty and rinse immediately after

completing each titration.