Triiodide Ion: Determination of an Equilibrium

Constant
Princess Gabrielle T. Libetario, Jenny S. Navarro, Cyra Austin S. Rico
BS Chemical Engineering
Xavier University-Ateneo de Cagayan

Abstract — The experiment, solvent extraction was done to Triiodine is usually formed in a solvent extraction
determine the equilibrium constant (Keq) in the formation conducted in a separatory funnel. Normally, water is used as a
of triiodide ion (I3-) that exists in equilibrium with iodine solvent while the other one is a hydrophobic or an organic
(I2) and iodide ion (I-). Distribution constant of iodine solvent. Hence, the distribution constant is a measurement of
between two immiscible liquids in the extraction was how hydrophilic/hydrophobic a chemical substance is. [2]
obtained at different concentration of organic solution. Extraction is used to separate substances like
The concentrations of the products and reactants at isolating or purifying a product for rapid and clean separation
equilibrium were obtained through titrating with Na2S2O3. of both organic and inorganic substances by using a separation
The average distribution constant value of I2 in CH2Cl2 funnel. Distribution of a solute between two immiscible liquid
and H2O was 65.77. The equilibrium constant was phases is involved in this procedure. Elemental iodine can be
determined through the concentration obtained for both easily dissolved in a carbon tetrachloride and the solubility in
products and reactants with the average value of 1326.08. water can be increased by the addition of potassium iodide.
Keq is greater than 1 which means that it is a spontaneous The molecular iodine reacts reversibly with negative ion, thus
reactions that favors the formation of the products. creating the triiodide anoin, I3-, which dissolves well in water.
[3]

Keywords - Solvent extraction, Hydrophilic, Hydrophobic,

Distribution constant, Equilibrium constant II. EXPERIMENTAL SECTION

I. INTRODUCTION The preparation of the different concentration organic

solution was done first in the experiment. This includes
The equilibration of the aqueous solution with an immiscible weighing the desired amount of Iodine to be dissolved in an
organic phase to establish the equilibrium is an essential organic solvent, CH2Cl2, to obtain 0.080M, 0.040M and
feature in this experiment. It expresses the relationship 0.020M concentrations. After the organic solutions of I 2 in
between products and reactants of a reaction at equilibrium CH2Cl2 were prepared, 25ml of each different concentration
with respect to its specific unit. The reaction in determining solution was place in three different separatory funnel to
the Keq for the formation of triiodide ion in aqueous solution undergone solvent extraction with 100ml of H2O. This mixture
is: of two immiscible liquids was shaken properly and opening
I-(aq) + I2(aq) = I3-(aq) valve to let the pressure out from time to time. The mixture
was set to attain equilibrium for 10 minutes. After the mixture
[𝐼3− ]𝑎𝑞 attained its equilibrium which was marked by separation of the
𝐾𝑒𝑞 = aqueous and organic layer, both of this layer were extracted
[𝐼 − ]𝑎𝑞 [𝐼2 ]𝑎𝑞 separately in to two separate containers. Through pipet, 10ml
I2 (org) is the result in titrating a portion of the of each organic aliquot and 100ml of each aqueous aliquot
organic phase with thiosulfate. [1] Iodine crystals are was obtained and place in different 250 ml Erlenmeyer flask.
sparingly soluble in pure water but are way too soluble in In each flask, 10ml of 0.1N KI was added. This is followed
aqueous solutions of potassium Iodide (KI) owing to then by titration with standardized Na2S2O3. The volume of
formation of complex tri-iodide (I3-) ions which exist in the titrant were recorded and used to determine the
equilibrium with free iodine molecules and iodide ions. A concentration of I2. With the concentration of I2 in both
complex ion, the tri-iodide ion (I3-), is formed from the organic and aqueous obtained in this part, the distribution
reaction between I- and I2: constant is calculated.
The second part of the experiment made use of the
Water layer: I2(aq) + I-(aq) ↔ I3-(aq) remaining different concentration of I2 in CH2Cl2 which was
↕Kd previously made in the first part. The same procedure was
Organic layer: I2 (organic) followed except that instead of H2O in the solvent extraction,
in the second part of the experiment 100ml KI of varying
[𝐼2 ]𝑜𝑟𝑔 concentration was added. The same titrant was used, Na2S2O3.
𝐾𝑑𝑖𝑠𝑡 = The volume of the titrant was used to obtain the concentration
[𝐼2 ]𝑎𝑞
of the triiodide ion, iodine and iodide ion which exist in
equilibrium. The Equilibrium constant is then calculated by
the use of the obtained concentrations.
 III. RESULTS AND DISCUSSION (20 PTS) The distribution constant (Kd) is observed to be 1326.08. The
The extraction of solvent at a chemical equilibrium in the Kd and Keq in also independent in the amount of solute and
first part makes immiscible phases inside a separatory funnel. solvent.
The organic phase CH2Cl2 is denser that is why it is in the
bottom layer while the aqueous phase of H2O is at the top CH2CL2
layer. The layers are distributed with I2 dissolved first in (25 mL)
[I2]aq [I3-]aq [I-] aq Keq Keq(ave)
CH2Cl2. The aqueous phase is brownish due to the dipole or + M of
induce-dipole interaction. The distribution constant (KD) of I2 I2
between the two immiscible liquid is determined by adding KI 0.080 5.0 X 10-4 0.03 M 0.404 M 160.44
in the aliquots of two layers and titrating with Na2SO3, the -4 -3 M
following shows the reaction: 0.040 1.44 X 10 9.35 X 10 0.049 M 1315.83 1326.08
-5 -3 M
0.020 9.08 X 10 5.87 X 10 0.026 M 2501.97
2𝑆2 𝑂32− (𝑎𝑞) + 𝐼2(𝑎𝑞) ↔ 𝑆4 𝑂62−(𝑎𝑞) + 2𝐼 − (𝑎𝑞)
2𝑆2 𝑂32− (𝑎𝑞) + 𝐼3− (𝑎𝑞) ↔ 𝑆4 𝑂62−(𝑎𝑞) + 3𝐼3− (𝑎𝑞) IV. ERROR ANALYSIS (3 PTS)

The disappearance of the reddish-violet color of solution The low precision of the distribution method is clearly
indicates the endpoint in the titration of the organic layer observed from the data obtained. The main component in the
which means all iodine has been neutralized by thiosulfate. experiment is very volatile which is I2, it can easily escape,
Redox reaction happens between thiosulfate and iodine, the thus causes the concentration of the solutions to be lower than
thiosulfate being oxidized and the iodine being reduced. In its original. Rapid absorption of iodine can cause inaccuracy
table 1 summarizes the calculated KD at different amount of I2. of the volume in the experimental values and calculations.
Another source of errors would be human error such as bias
Table 1: Distribution Constant (KD) of I2 in CH2Cl2 and H2O reading of the volume and also instrumental error such as
M of I2 in [I2] [I2] aqueous KD KD(average) transferring of chemicals; some of the solution was lost or left
CH2Cl2 organic layer in the instrument.
layer
(25 mL)
0.080 0.13945 1.895 X 10-3 73.59 V. CONCLUSION (5 PTS)

0.040 0.0726 1.055 X 10-3 68.82 65.77

The distribution constant (KD) of I2 between 0.080M,
0.020 0.04365 7.95 X 10-4 54.91 0.040M, 0.020M concentrations of organic solution CH 2Cl2
and H2O has an average value of 65.77. With the average
distribution constant in the first part, the equilibrium constants
The average distribution constant (KD) is 65.77. It is (Keq) were obtained which by average is 1326.08. It shows the
dependent on the temperature and nature of Iodine and low precision of the distribution method due to its
independent on the two different concentrations. experimental errors such as the high volatility of iodine in the
organic solution and also human and instrumental errors. The
The next part deals also with solvent extraction method but KD and Keq were both dependent on the temperature and
instead of adding water in the solution of I2 and CH2Cl2, nature of the substance which is iodine, a volatile chemical,
different concentrations of KI is added to extract most of the but independent from the different concentrations.
Iodine into the KI solution layer. Therefore, the amount of the
iodine present in the organic aliquot is less than the amount
present in the KI aliquot. The aqueous layer contains most of REFERENCES
the iodine and triiodide ion.
[1] http://pubs.acs.org/doi/pdf/10.1021/ed055p795 (Accessed
The iodine and triiodine is mostly contained in the aqueous
layer. The iodine present in the aqueous layer is the iodine that December 15, 2017)
the KI extracted from the solution and reacted with thiosulfate. [2] S. P. Mushtakova, G. V. Gerasimova, and T. M.
The difference between the amount of iodine present in the
Varlamova “Distribution of Iodine in the dine–Water–
aqueous layer and the concentration obtain from reaction of
sulfate is the concentration of triiodine ion. The titration of the Chloroform (Dichloromethane) and Iodine–Potassium Iodide–
aliquots and the indication of end point is the same in the first Water–Chloroform (Dichloromethane)”, Journal of Analytical
part. The equilibrium constant was then solved given with the Chemistry 2009, 64, 125- 28. Retrieved Jan. 3, 2018
necessary data. The result obtain shown in table 2.
[3] https://www.slideshare.net/adujoy/triiodide (Accessed
Table 2: Equilibrium Constant of Iodine December 15, 2017)
 APPENDICES
Solving for 0.1 M Na2S2O3:
158.1 𝑔
(0.1 𝑀)(0.250𝐿) = 0.025𝑚𝑜𝑙 𝑁𝑎2 𝑆2 𝑂3 × 𝑁𝑎2 𝑆2 𝑂3 = 3.9252𝑔 𝑁𝑎2 𝑆2 𝑂3
𝑚𝑜𝑙
Solving for 0.30M and 0.15M KI:
Let X= either 0.30M or 0.15M
166 𝑔
(𝑋)(0.100) = 𝑌 𝑚𝑜𝑙 𝐾𝐼 × = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐾𝐼 𝑛𝑒𝑒𝑑𝑒𝑑
𝑚𝑜𝑙
PART A: DETERMINATION OF THE DISTRIBUTION CONSTANT OF I 2 IN CH2Cl2 AND WATER
Table 1.1

CH2Cl2 layer H2O layer

M of I2 in Volume of 0.1 Volume of 0.1
Volume of Volume Volume
Run No. CH2Cl2 (25 M Na2S2O3 M Na2S2O3
H2O (mL) aliquot (mL) aliquot (mL)
mL) (mL) (mL)
1 0.080 100 10 27.89 100 3.79
2 0.040 100 10 14.52 100 2.11
3 0.020 100 10 8.73 100 1.59
Actual mass of 0.30 M KI: 4.986 g
Actual mass of 0.1 M Na2S2O3: 3.950 g
STOICHIOMETRIC RATIO
Aqueous layer: 1 mol I2total / 2 mol S2O32-
Organic layer: 1 mol I2 / 2 mol S2O32-
CONCENTRATION OF I2 IN CH2Cl2, THE ORGANIC LAYER:
1𝐿 0.1 𝑚𝑜𝑙 𝑁𝑎2 𝑆2 𝑂3 1 𝑚𝑜𝑙 𝐼2 (𝐶𝐻2 𝐶𝑙2 )
(27.89 𝑚𝐿 𝑁𝑎2 𝑆2 𝑂3 ) ( )( )( 2 𝑚𝑜𝑙 𝑆 𝑂 )
103 𝑚𝐿 𝐿 2 3−
For run1: [I2 (CH2Cl2)] = 1𝐿
(10 𝑚𝐿 𝑎𝑙𝑖𝑞𝑢𝑜𝑡)( 3 )
10 𝑚𝐿

[I2 (CH2Cl2)] = 0.13945M

CONCENTRATION OF I2 IN H2O, THE AQUEOUS LAYER:
1𝐿 0.1 𝑚𝑜𝑙 𝑁𝑎2 𝑆2 𝑂3 1 𝑚𝑜𝑙 𝐼2 (𝐶𝐻2 𝐶𝑙2 )
(3.79 𝑚𝐿 𝑁𝑎2 𝑆2 𝑂3 ) ( )( )( 2 𝑚𝑜𝑙 𝑆 𝑂 )
103 𝑚𝐿 𝐿 2 3−
For run1: [I2 (aq)] = 1𝐿
(100 𝑚𝐿 𝑎𝑙𝑖𝑞𝑢𝑜𝑡)( 3 )
10 𝑚𝐿

[I2 (aq)] = 1.895X10-3 M

[(𝐼2 )(𝐶𝐻2 𝐶𝑙2 )}
DISTRIBUTION CONSTANT (KD) = [(𝐼2 )𝑎𝑞]

0.13945𝑀
KD = = 73.59
1.895𝑥10−3 𝑀

73.59+68.82+54.91
KD(average) =
3

KD(average) = 65.77
 M of I2 in CH2Cl2 [I2] organic layer [I2] aqueous layer KD KD(average)
(25 mL)
0.080 0.13945 1.895 X 10-3 73.59 65.77
0.040 0.0726 1.055 X 10-3 68.82
-4
0.020 0.04365 7.95 X 10 54.91

PART B: DETERMINATION OF EQUILIBRIUM CONSTANT

TABLE 2
CH2Cl2 layer H2O layer
Volume of 0.1 Volume of 0.1
CH2Cl2 (25 Volume of KI Volume Volume
Run No. M Na2S2O3 M Na2S2O3
mL) + M of I2 (100 mL) aliquot (mL) aliquot (mL)
(mL) (mL)
1 0.080 0.15 10 16.30 100 65.89
2 0.040 0.15 10 5.33 100 18.99
3 0.020 0.30 10 3.50 100 11.94
Actual mass of 0.30 M KI: 4.986 g
Actual mass of 0.15 M KI: 2.495 g
Actual mass of 0.1 M Na2S2O3: 3.950 g

CONCENTRATION OF I2 IN CH2Cl2, THE ORGANIC LAYER:

1𝐿 0.1 𝑚𝑜𝑙 𝑁𝑎2 𝑆2 𝑂3 1 𝑚𝑜𝑙 𝐼2 (𝐶𝐻2𝐶𝑙2 )
(16.30 𝑚𝐿 𝑁𝑎2 𝑆2 𝑂3 ) ( )( )( 2 𝑚𝑜𝑙 𝑆 𝑂 )
103 𝑚𝐿 𝐿 2 3−
For run1: [I2 (CH2Cl2)] = 1𝐿
(10 𝑚𝐿 𝑎𝑙𝑖𝑞𝑢𝑜𝑡)( 3 )
10 𝑚𝐿

[I2 (CH2Cl2)] = 0.0815M

CONCENTRATION OF I2 IN H2O, THE AQUEOUS LAYER:
1𝐿 0.1 𝑚𝑜𝑙 𝑁𝑎2 𝑆2 𝑂3 1 𝑚𝑜𝑙 𝐼2 (𝐶𝐻2 𝐶𝑙2 )
(65.89 𝑚𝐿 𝑁𝑎2 𝑆2 𝑂3 ) ( )( )( 2 𝑚𝑜𝑙 𝑆 𝑂 )
103 𝑚𝐿 𝐿 2 3−
For run1: [I2 (aq) + I3-(aq)] = 1𝐿
(100 𝑚𝐿 𝑎𝑙𝑖𝑞𝑢𝑜𝑡)( 3 )
10 𝑚𝐿

[I2 (aq) + I3-(aq)] = 0.032945 M

CALCULATION OF I2(aq) FROM THE DISTRIBUTION CONSTANT CALCULATED IN PART A

[(𝐼2 )𝑖𝑛 𝐶𝐻2 𝐶𝑙2 ] 0.0815 𝑀

[I2aq] = = = 5.0𝑥10−4 𝑀
𝐾𝐷 65.77

CALCULATION FOR THE TRIIODIDE ION, [I3-(aq)], BY SUBTRACTING [I2(aq)] FROM [I2 (aq) + I3-(aq)]

[I3-(aq)] = [I2 (aq) + I3-(aq)] - [I2(aq)]

[I3-(aq)] = 0.032945 M – 5.0X10-4 M = 0.032445 M

CALCULATION FOR THE [I-(aq)] FROM [I2]initial AND [I3-(aq)]

[I-(aq)] = [I2]initial - [I3-(aq)]

[I-(aq)] = 0.080 M – 0.032445 M = 0.40445 M

CALCULATION FOR THE EQUILIBRIUM CONSTANT

[𝐼3− (𝑎𝑞)]
Keq =
[𝐼2(𝑎𝑞) ][𝐼 −(𝑎𝑞)]

0.032445 𝑀
Keq = (5.0𝑋10−4
𝑀)(0.40445 𝑀)

Keq = 160.44

160.44+1315.83+2501.97
KD(average) =
3

KD(average) = 1326.08

CH2CL2 (25 [I2] org [I2 + I3-]aq [I2]aq [I3-]aq [I-] aq Keq Keq(ave)
mL) + m of I2
0.080 0.1395 M 0.03 5.0 X 10-4 0.03 M 0.404 M 160.44 1326.08
-3 -4 -3 M
0.040 0.0726 M 9.49 X 10 1.44 X 10 9.35 X 10 0.049 M 1315.83
0.020 0.0437 M 5.97 X 10-3 9.08 X 10-5 5.87 X 10-3 M 0.026 M 2501.97