DATE PERFORMED: AUGUST 24, 2011

QUANTITATIVE DETERMINATION OF COPPER CONCENTRATION IN

AQUEOUS SOLUTION BY IODOMETRIC TITRATION

J.M.F. UAYAN
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY, PHILIPPINES
RECEIVED AUGUST 31, 2011

ABSTRACT

The objective of the experiment was to determine the copper concentration in an aqueous solution
using a redox titration called iodometry. A standard Copper solution was made using 15.62g of pure
Copper sulfate pentahydrate. A working standard of Copper solution was then prepared. A thiosulfate
solution was then standardized and used as a titrant. A 50ml Copper solution sample was obtained and
three 10ml aliquots were taken. The aliquots were then titrated with the standardized thiosulfate solution
and the initial and final volumes were recorded. The concentration of Cu(II) ions were then calculated.
Means 0.161 M and 10230 ppm, ranges 0.036 and 2288, and confidence limits 0.16M ± 0.05M and 10000
ppm ± 3000 ppm were obtained (molarity and ppm respectively). The calculated RSD’s 124.068 ppth and
124.883 ppth show that bad precision was obtained.

INTRODUCTION Iodine has a low solubility in water and it is

There are two types of redox reactions involving
the substance Iodine, Iodimetry and Iodometry.
Iodimetric titration involves a direct titration of a
reducing analyte with Iodine. In Iodimetry, there
is only one reaction present in the titration
process.
( )
[1]
( )
volatile. Because of its volatility, amounts of
Iodine can be lost in the solution. In excess
Iodide, the Iodine reacts with Iodide to form a
triiodide complex. Reaction [3] allows one to
obtain useful concentrations of Iodine in
aqueous solution. Reaction [3] lowers the free
concentration of I2 and the solution is stable
enough to titrate. Thus, it is beneficial to have
excess iodide in the solution.
[3]

However, there are only few reducing agents The triiodide solution is then titrated with a
strong enough to reduce Iodine. Because of this, standardized Thiosulfate solution, a reducing
there are only few titrations that involve agent. The Thiosulfate solution reduces the I3-
iodimetry. back to Iodide.

In an Iodometric titration, an oxidizing analyte is

made to react with Iodide to produce Iodine. [4]

( ) Drops of freshly prepared starch solution are

[2]
added to indicate the endpoint, as I2 (I3- in
( ) aqueous solutions) bonds with the starch
forming a blue-black complex. Titration is
continued until the blue-black color disappears.
The blue-black color, however, may reappear
because of the oxidation of the excess I- with the
air. The volume of the standardized Thiosulfate
used is measured, and if all the required
calculations go smoothly, one can accurately
calculate the concentration of the copper present
in the aqueous solution.
RESULTS AND DISCUSSION
In this experiment, the analyte is copper (in the
form of CuSO4•5H2O), which is strong enough
to oxidize Iodide ions to Iodine. 1:1 (v/v) NH3
was then added dropwise to precipitate out the
Cu(II) ions. It is important not to add the NH3 in
excess because [Cu(NH3)4]2+ interferes with the
reduction of Cu2+ and changes the pH of the
solution, which also interferes (slows) with the
reaction. To prevent this, 1-2 drops of Glacial
acetic acid was added to counter the pH change
caused by the added NH3 and to dissolve the
precipitate formed. I-„s (in the form of KI) were
then added in excess to ensure that all of the
Cu2+‟s in the solution would be reduced. After
the addition if KI, it is important that the
solution must be titrated immediately because
the excess I- can be oxidized by the air and this
leads to a positive error. The oxidation of Iodide
by Cupric ions is shown below:
[5] ( )
The reaction proceeds rapidly in slightly acidic
to neutral solutions. The reaction proceeds very
slowly in strongly basic or acidic solutions.
The I2 produced will then react with the excess I-
to form I3- shown in [3]. KI is also added to
ensure that the iodine (low solubility in water)
produced by [5] will react with the excess I- to
form I3-.
The I3- is then titrated with the standardized
Thiosulfate solution. The reaction is shown in
[4]. In the preparation of the standard
Thiosulfate, it is important to boil the distilled
water that will be used to dissolve the
Thiosulfate. Even distilled water that was left
standing for a period may have dissolved enough
CO2 that can lower the pH sufficiently leading to
the decomposition of Thiosulfate ions to Sulfur.
It is also important to add some solid Na2CO3 in
the solution. Na2CO3 raises the pH slightly that
prevents bacteria from growing (that may
metabolize the Thiosulfate ions) if the solution is
left to stand for a period.
To indicate the endpoint of the titration, drops of
starch solution must be added. It is important
that the starch solution is freshly prepared so
that it has not yet decomposed slowly and its
sensitivity (its ability to bond with I2) has not yet
decreased. It is also important to delay the
addition of starch until almost all of the I2 (I3- in
aqueous solutions, refer to reaction [3]) is
reduced to I- because the disappearance of the
blue-black will be gradual. In addition, the
presence of the excess of I- (the product of
reaction [4]) increases the sensitivity of the
starch indicator. That is also the reason why KI
was added in excess.
However, the precipitate formed in reaction [5],
CuI(s), adsorbs I2 (I3- in aqueous solutions) which
causes a dull endpoint (the color change near the
equivalence point is gradual, i.e. the endpoint
has already been reached but the color change is
undetected). This can be prevented by adding
CNS-, for CNS- displaces the adsorbed I2, shown
below:
[6]
The addition of CNS- makes the endpoint
sharper because I2 is now available for bonding
with the starch indicator. The disappearance of
the blue-black color must last for at least 30
seconds or the titration has not reached the
endpoint yet. The disappearance is always
temporary as the excess I- will react with O2 in
the air leading to the production of I2, which will
be detected by the starch and hence the blue-
black color will reappear. The reaction is shown
below:
[7] ( )
Table I. Standardization of Sodium Thiosulfate
Solution
Trial # Net volume of Thiosulfate (mL)
1 15.3
2 4.6
3 10.7
As one can see, the data gathered is very
inconsistent. The large differences on the titrant
used can be explained by many factors. One of
the factors is color change detection. Since the
data from this experiment came from the whole
class (i.e. each trial is done by a different
person), the ability to detect slight color changes
varies from person to person (e.g. their
definition of light brown/ tan or any other color
differ), thus their “endpoint” also varies, which
results to these large differences in the titrant
used. Another factor is the solution preparation.
Since these data came from different groups and
each group has to prepare their own “working
standard” of Cu(II) solution, there is a large
chance that the prepared solutions really did
differ in their molarities (some groups may have
committed errors during the solution preparation
while others did not).
Table II. Sample Analysis
Trial # Net volume of Thiosulfate (mL)
1 24.0
2 23.6
3 29.35
Compared to the standardization of the titrant,
the data from the sample analysis are much more
precise. However, the same difficulties were
encountered and many trials were wasted.
Concentrations (in Molarity) 0.151 M, 0.148 M,
and 0.184 M were calculated from trials 1, 2,
and 3 respectively. A range of 0.036, RSD of
124.068 ppth were obtained. Based on the
calculated statistical parameters, the precision is
not that great. The accuracy of the experiment
cannot be determined yet because the actual
amount the Cu2+ concentration in the sample
was not disclosed.
There are many sources of error in the
experiment. A source of error is CuI(s) (a product
of reaction [5]) forms a weak complex with I2. If
this happens, there will be less I2‟s that would be
available to react with Thiosulfate and hence, a
negative error would be obtained. This can be
prevented by adding SCN- ions just before the
titration has reached its endpoint. Another
source of error is I2 is volatile and some amounts
of I2 may evaporate before titration resulting into
a negative error. This can be prevented by
adding excess I- because I2, together with I-,
forms I3-, a more stable complex. Also, one can
perform Iodometric titration using cold solutions
so that the evaporation is minimized. Another
source of error is in acidic solutions, the excess
I- can be easily oxidized in to I2 resulting in a
positive error. Titrating the solution immediately
with the standard Thiosulfate solution can
prevent such unnecessary oxidation. Another
source of error is adding a large amount of
excess NH3. Even though the NH3 can be
neutralized by adding Glacial acetic acid, the
NH4CH3COO formed may interfere with
reaction [5], resulting in a negative error. This
can be prevented by adding NH3 dropwise and
one should observe if the solution changes for
every each drop added.
CONCLUSIONS AND
RECOMMENDATIONS
Although the data was very inconsistent, the
method is successful in determining the
concentration of cupric ions in an aqueous
solution. The procedure for this experiment can
be made better. The lab manual states, “After the
addition of KI, the solution must be titrated until
the brown color almost disappears”. This
statement needs a revision because if the brown
color almost disappears, the solution is already
overtitrated with Thiosulfate ions. Other sources
indicate that one must stop the titration if the
color of the solution turns light brown/tan
(completely different from almost disappeared)
to add the starch indicator. With more trials, the
RSD and Confidence limit interval would
become much smaller and one can find a more
precise value of the concentration of Cu2+ ions in
the sample.
It is also recommended that the Thiosulfate
solution must be standardized using another kind
of titration that does not involve iodine. This
procedure is more precise than the one indicated
on the lab manual. Then after the
standardization, one can proceed to the copper
analysis part. The procedure indicated by the lab
manual for this experiment leads to many
systematic errors.
[5] Kimsley, V.S.: Introductory Chemistry, 2nd
Ed. Brooks/Cole Publishing Company,
California. 1995
[6] Skoog, D.A., West, D.M., Holler, F.H.,
Crouch, S.R.: Fundamentals of Analytical
Chemistry, 8th Ed. Brooks/Cole Publishing
Company, California, 2004.

If one wants to determine the concentration of
cupric ions in an aqueous solution, he/she may
use spectrophotometry, which is faster and
highly more sensitive than iodometry. This
method is based on the formation of
[Cu(NH3)4]2+. Unlike in iodometry, excess NH3
is added to allow the formation of the complex
and using Beer‟s law and a blank solution, one
can accurately determine the actual Cu2+
concentration in the aqueous solution.
APPLICATIONS
 Determination of the amount of copper
in a brass alloy sample.
 Determination of the %H2O2 in Agua
Oxigenada bottles (antiseptic).
 Determination of IO3- and IO4- present
in Aminophenols.
 Determination of Oxygen content of
H2O samples.
REFERENCES
[1] Petrucci, P.H., Herring, F.G., Madura J.D.
and Bissonnette C.: General Chemistry,
Principles and Modern Application, 10th Ed.
Prentice Hall, New Jersey, 2010
[7] Gregersen, E.: The Britannica Guide to
Statistics and Probability, 1st Edition. Rosen
Educational Publishing, 2010
[8] Peter, A., Shriver: Inorganic Chemistry:
Shriver and Atkins, 4th Edition. Oxford
University Publishing, 2006
[9] Kimura, M., Ikawa R., Shiota, Y.,
Tsukahara, K. “Kinetics and Mechanism of the
Copper(II)-Catalyzed Oxidation of Iodide Ion by
Chromate (VI) Ion in Aqueous Solution”. The
Chemical Society of Japan, Volume 71, pp. 893-
897.
[10] Christian, G.D.: Analytical Chemistry, 6th
Edition. Wiley Publishing, New York, 2003.
APPENDIX
A. WORKING EQUATIONS
∑
∑ ( )
√

[2] Rosenberg, J.L., Epstein, L.M.: College

Chemistry, 7th Ed. McGraw-Hill, Inc., New
York, 1990
√
[3] Brown, T.L., Le May Jr., H.E., Bursten,
B.E.: Chemistry the Central Science, 11th Ed.
Prentice Hall, New Jersey, 2010.

[4] Mortimer, C.E.: Chemistry, 6th Ed.

Wadsworth Publishing Company, 1986
 2nd Trial:

3rd Trial:
Where:
is the mean;
n is the number of measurements taken;
s is the standard deviation;
RDS is the relative standard deviation; Average [Cu2+]:
R is the range;
RR is the relative range;
CL is the confidence limit (95%);
[S2O32-] is the molarity of S2O32-;
[Cu2+] is the molarity of Cu2+; Titer Cu2+:
T Cu2+ is the titer of Cu2+ in mg/ml;
Ppm Cu2+ is the concentration of Cu2+ expressed
in mg/L.

B. SAMPLE CALCULATIONS

Standardization of S2O32-:
1st Trial:
Determination of ppm Cu2+:

1st Trial:

2nd Trial:

2nd Trial:

3rd Trial:

3rd Trial:
Average [S2O32-]:

̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ Average ppm Cu2+:

Determination of Cu2+ concentration:

1st Trial:
Statistical Parameters for [Cu2+]: Relative Standard Deviation:

Range:

Standard deviation: Confidence Limit:

∑ ( )
√ √

√
( ) ( ) ( )
√

The pooled standard deviation cannot be

Relative Standard Deviation: calculated because the data gathered came from
the whole class (i.e. the parts of the data came
from different groups).

Confidence Limit:

Statistical Parameters for ppm Cu2+:

Range:

Standard Deviation:
∑ ( )
√

( ) ( ) ( )
√