Experiment 6

Title Estimation of copper percentage present in brass sample

Introduction

Brass (tembaga) is an alloy of copper (around 60%) and zinc (around 40%).Both Cu and Zn
metals get converted into their nitrates when dissolved in concentrated nitric acid producing
reddish brown fumes of oxides of nitrogen.
Cu + 4HNO 3 → Cu (NO 3 ) 2 + 2H 2 O + 2NO 2 
2Cu 2 + + 4KI → Cu 2 I 2  + 4K + + I 2 

Since oxides of nitrogen are also good oxidizing agents they cause liberation of extra iodine from
the brass solution. Therefore they have to be destroyed by adding urea.
2NO 2 + H2O → HNO3 + HNO2 → NH2CONH 2 + 2HNO2 → CO 2 + 2N2 + 3H2O
(ni tri c a ci d) (ni trous a ci d) (ure a)

The excess of nitric acid present in the brass solution is neutralized by adding ammonium
hydroxide solution till a pale blue precipitate of cupric hydroxide Cu(OH)2 is obtained; otherwise
nitric acid (oxidizing agent) can cause liberation of KI.
Dissolved oxygen liberates extra I2 by oxidizing Cu2I2 to CuI2 which is unstable and changes into
Cu2I2 and I2. This results in higher titer value which is more than the equivalent amount of Cu 2+
ion present in the solution.
The brass solution should not be alkaline before adding KI because Cu2+ precipitates as Cu(OH)2
which does not liberate I2. Hence I2 liberated will be less than the equivalent amount of Cu2+ ion
present in the solution. Therefore the solution is made weakly acidic by adding acetic acid before
adding KI. This maintains a pH of 4 to 5.5 and helps in best result.
Cupric nitrate Cu(NO3)2 liberates equivalent quantity of iodine by oxidation when excess of KI is
added to brass solution.
2Na 2 S 2 O 3 + I 2 → Na 2 S 4 O 6 + 2Na I
(s odi umte tra thi ona te)
The iodine liberated is titrated against sodium thiosulphate solution using starch as the indicator.
Starch indicator is added near the end point and not in the beginning – in the initial stages there
is high concentration of iodine which then forms strong starch – iodine complex.
Iodine also gets adsorbed on colloidal starch particles in the starch solution. The adsorbed iodine
is not easily available for reaction with hypo; it leads to higher titre value. Thus adding starch
near the end point minimizes the error.
Chemicals/ • Brass 1g each group
Materials • Concentrated HNO3
• Sodium thiosulphite (0.05N)
• Urea 1g each group
• NH4OH solution
• Acetic acid
• KI 10%
• Starch indicator

Apparatus • Volumetric flask 250 ml

• Conical flask 250 ml
• Burette
• Retort stand and burette clamp.
• Wooden Clip holder
• Test tube
• Dropper
• Pipette
• Weight
• Measuring cylinder
• Hot plate
• pH meter

Procedure 1. Weight 1 g of brass and delicately cut into thin strips. Then, place into a 250
ml conical flask.
2. Add 10 ml of concentrated HNO3 into the conical flask to dissolve the brass
(reddish brown fumes of oxides of nitrogen occur). Add another 10 ml of
concentrated HNO3 if the brass still has not dissolved yet (maximum volume
allow for HNO3 is 30 ml).
3. Then add in 1 g of urea followed by 30 ml of distilled water and boil for 1 to 2
minutes (blue pale solution occurs).
4. Cool the solution. Then transferred the solution into the volumetric flask of
250 ml and add the distilled water until up to the mark.
5. For estimation of copper in brass solution, pipette out 10 ml of brass solution
into the conical flask and add NH4OH solution drop by drop (while swirl the
conical flask continuously) to remove excess nitric acid. Stop dropping
NH4OH solution when pale blue precipitate of cupric hydroxide Cu(OH)2 is
 obtained. *If not ensure pH around 7.0 - 8.5 (weak base).
6. Then drop acetic acid (pH 4.5 - 5.5 weak acid) to dissolve the precipitate and
to ensure the solution is in acidic media followed by dropping 10% KI until
brown cloudy solution occurs.
7. Fill in the burette with standard sodium thiosulphite (0.05N).
8. Then, titrate the solution (obtained from step 6) with standard sodium
thiosulphite (0.05N) until light yellow colour is obtained.
9. After that, add 1 ml of starch indicator and continue the titration by adding
drop wise until the light yellow colour just disappear and get milky white
precipitate (cuprous iodide).

Result

Strength of Na2S2O3 solution N1 = 0.05N

Weight of brass sample taken = _______g

Final burette reading

Initial burette reading
Volume of Na2S2O3 in mL

Questions 1. Calculate the copper weight in 250 ml of brass solution.

2. Calculate the percentage of copper in brass solution.

3. Explain why blue pale colour solution is obtained when urea is added to the
dissolve brass solution.

Reference 1. Ferrari, Jean & Panossian, Zehbour & Almeida, M.B. (2004). Determination of
copper and zinc contents in brass plating solutions by titrimetric analysis: A
review. Transactions of the Institute of Metal Finishing. 91. 38-43.