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Exercise 14 Prelab:
Iodometric Determination of Copper Postlab:
Unknown Number:___ Accuracy:
Precision:

I. Objectives
At the end of the exercise, the student should be able to:
1. Determine the amount of copper ina given sample; and
2. Apply the proper techniques of iodometry in the analysis of copper.

II. Principles
The copper content of ares and alloys such as bronze and brasses as usually determined
with the use of iodometry. Posibble interferences are eliminated through appropriate preparation
of the sample solution (Falardo, 2009). The steps taken are:
1. Sample is first dissolved in nitric acid (HNO3)
2. pH of the sample is adjusted to 3.5-4.5, with the use of a buffer solution
3. Cupric ions (Cu2+) present in the sample solution are iodometrically reduced to
Cuprous Iodide (CuI)
4. Iodine that is formed in the reduction of cupric ions is then titrated with a standard
solution of sodium thiosulfate.
To elaborate futher on these steps, first, the sample is dissolved in nitric acid (HNO3).
This produces N2O, NO, and HNO2 which should all be removed since they promote the air
oxidation of iodine which can give a positive error to the amount of copper to be analyzed. A
good way to remove these include fuming with concentrated sulphuric acid (H2SO4), or, if the
sample easily dissolves in nitric acid, simply boiling with urea can remove the nitrous acid and
oxides of nitrogen, as according to the reaction:

Equation 14.1

The second step is to buffer the solution. The analysis of copper is usually best done at around
the pH range of 3.5-4.5, where an acetic acid buffer can be used. This ph range prevents the
formation of pentavalent arsenic and antimony, which can oxidize iodide (Harris, 2010). A high
pH may also cause the hydrolization of cupric ions (equation 14.2), or cause the precipitation of
Cu(OH)2, which would decrease the oxidizing strenght of the solution and give a negative error
in the titration.

Equation 14.2

Copper ores also contain iron which can interfere with the analysis since it also oxidizes iodide
and can give a positive error in the amount of copper (Equation 14.3). This can be prevented by
removing iron through precipitation with ammonia, since copper forms a soluble complex with
ammonia (Cu(NH3)4 2+) and remains in the solution. This however, can also be erroneous since
copper compounds can co-precipitate with ferrous hydroxide. An alternative method is the park
 method where ferric is complexed with flouride to form FeF6 3-, which decreases the oxidizing
strenght of ferric and prevent the oxidatiopn of iodine.

Equation 14.3

The reaction of iodide and cupric ions is quantitative and favored by the precipitation of cuprous
iodide (Equation14.4), which makes the method useful for macro amounts of copper (Skoog,
2013). Iodide released in the reaction will be titrated with standard sodium thiosulfate (Equation
14.5) without removing the cuprous iodide precipitate. The precipitate, however, adsorbs iodine
which can be minimized by the addition of thiocyanate just before the endpoint since the adsorbed
iodine is released at the endpoint (Equation 14.6). Thiocyanate is added just before the endpoint
since the iodine oxidizes thiocyanate and can give a negative error to the amount of copper in the
analysis.

Equation 14.4
Equation 14.5
Equation 14.6

An im portant note is that the equivalent weight of copper is its formula weight because the actual
measurement step involves only a single electron change in the iodometric reduction.

Sources:

Fajardo, N. N.,et. al. (2009) CHEM 32.1: Quantitative Inorganic Analysis Laboratory. 4th
Revision. University of the Philippine Los Baños: Institute of Chemistry. (pp. 50-52)

Harris, D. C. (2010) Quantitative Chemical Analysis. 8th Edition. New York: W. H. Freeman and
Company. (pp. 351)

Skoog, D. A. , et.al, (2013) Fundamentals of Analytical Chemistry. 9th Edition. Cengage Learning.
(pp. 442-445)

III. Prelab Calculations and Formulas

Mass of Copper
𝑔
𝐹𝑊𝐶𝑢 63.545
𝐸𝑊𝐶𝑢 = = 𝑚𝑜𝑙 = 63.545
𝑛 𝑒𝑞
1
𝑚𝑜𝑙
𝑚
(𝐸𝑊 𝑥 𝑉)𝐶𝑢 = (𝑁𝑉)𝑁𝑎2 𝑆2𝑂3 Eq. 14.6
 (𝑁𝑉)𝑁𝑎2 𝑆2 𝑂3 𝑥 𝐸𝑊𝐶𝑢
𝑚 𝐶𝑢 =
𝑉𝐶𝑢
𝑚 𝐶𝑢
% 𝐶𝑢 = 𝑚 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100 Eq. 14.7

𝐹𝑊 𝐶𝑢𝑂
𝑚 𝐶𝑢𝑂 = 𝑚 𝐶𝑢 𝑥 Eq. 14.8
𝐹𝑊 𝐶𝑢
𝑚 𝐶𝑢𝑂
% 𝐶𝑢 = 𝑚 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100 Eq. 14.9

IV. Data and Results

Table 12.1. Analysis of Copper.
N of Standardized 𝑁𝑎2 𝑆2 𝑂3 Solution
Trial 1 Trial 2
Weight of container + sample, g
Weight of container - sample, g
Weight of container + sample, g
𝑁𝑎2 𝑆2 𝑂3solution
Initial Buret Reading, mL
Final Buret Reading, mL
Volume of 𝑁𝑎2 𝑆2 𝑂3 solution used, mL
% Cu, (w/w)
Average %Cu ± d , (w/w)
% CuO, (w/w)
Average %CuO ± d , (w/w)

V. Answers to the Prelab Questions

1. Why must urea be added during sample treatment?
2. What are the interferences in copper determination by iodometry? Give the ways
to minimize their effects.
3. What is the purpose of adding acetic acid after ammonia is added to achieve the
royal blue color?
4. It is advised that you work with one sample at a time just before KI is added to the
sample. Explain why?