KWAME NKRUMAH UNIVERSITY OF SCIENCE AND TECHNOLOGY, KUMASI

KNUST
COLLEGE OF SCIENCE

DEPARTMENT OF CHEMISTRY

ANALYTICAL LABORATORY REPORT

TITLE: DETERMINATION OF THE EQUILIBRIUM CONSTANT FOR THE

FORMATION OF TRI-IODIDE ION (I3-)

NAME: AUGUSTINE ADU

DATE: 23RD SEPTEMBER, 2014

E-mail :adu.aug@gmail.com

pg. 1
AUGUSTINE ADU-KNUST
E-mail:adu.aug@gmail.com
 DETERMINATION OF THE EQUILIBRIUM CONSTANT FOR THE
FORMATION OF TRI-IODIDE ION (I3-)
AIMS AND OBJECTIVES:
 To determine the equilibrium constant for the formation of tri-iodide ion
 To determine the partition coefficient of iodine between water and N- Hexane
 To demonstrate solvent extraction
INTRODUCTION
Solvent extraction is a very common laboratory separation procedure used when isolating or purifying a product.
It is extremely useful for very rapid and clean separation of both organic and inorganic substances. It involves
the distribution of a solute between two immiscible liquid phases. A separation funnel is used for this process.
The density of the phases must differ appreciably so that they can separate easily after mixing. The organic
solvent used for extraction must meet the following criteria:
 Should readily dissolve substances to be extracted.
 Should not react with the substance to be extracted.
 Should not react with or be miscible with water.
 Should have a low boiling point so it can be easily evaporated.
 Should be less viscous
Elemental iodine dissolves easily in carbon tetrachloride but its solubility in water can vastly be increased by the
addition of potassium iodide. The molecular iodine reacts reversibly with the negative ion, thus creating the
triiodide anion, I3−, which dissolves well in water. This is also the formulation of some types of medicinal
(antiseptic) iodine, although tincture of iodine classically dissolves the element in alcohol. The deep blue colour
of starch-iodine complexes is produced only by the free element.
In a chemical reaction, the whole of the reactants do not get converted into the products. After some time, there
will come a point when a fixed amount of reactants will exist in harmony with a fixed amount of products, the
amounts of neither changing anymore. This is called chemical equilibrium. The equilibrium constant for a
reaction is indeed a constant, independent of the activities of the various species involved, though it does depend
on temperature as observed by the Van’t Hoff equation. Adding a catalyst will affect both the forward reaction
and the reverse reaction in the same way and will not have an effect on the equilibrium constant. The catalyst
will speed up both reactions thereby increasing the speed at which equilibrium is reached. In the fields of organic
and medicinal chemistry, a partition or distribution coefficient (KD) is the ratio of concentrations of a compound
in the two phases of a mixture of two immiscible solvents at equilibrium. It is concentration equilibrium
constant, representing the equilibrium constant for the process of a compound, which begins in the mobile phase
and is dissolved into the solution (stationary) phase. The distribution equilibrium in the simplest case involves
the same molecular species in each phase. A(aq) = A(org)
Hence these coefficients are a measure of differential solubility of the compound between these two solvents.
Normally one of the solvents chosen is water while the second is hydrophobic (an organic solvent). Hence both
the partition and distribution coefficient are measures of how hydrophilic or hydrophobic a chemical substance
is. Partition coefficients are useful in estimating distribution of drugs within the body.
Iodine (I2) is sparingly soluble in pure water but dissolves it readily in aqueous solutions of potassium iodide
(KI) owing to the formation of complex tri-iodide (I3 -) ions which exist in equilibrium with free iodine
molecules and iodide ions.
I2 + I- ⇌ I3 –

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AUGUSTINE ADU-KNUST
E-mail:adu.aug@gmail.com
A complex ion, the tri-iodide (I3−) ion, is formed from the reaction between I− and I2. In the two-phase system
two equilibria occur simultaneously, each competing for I2
The concentration of all species at equilibrium can be determined titrimetrically, and the equilibrium constant
for the formation of the complex ion can be calculated. Titration of the aqueous layer gives the total iodine
present in the aqueous layer, that is,

[I2(total)] = [I2(aq)] + [I3−(aq)]

but [I2(aq)] = [I2(organic)] / K′
[I3−(aq)] = [I2(total)] – [I2(aq)]
[I−(aq)] = [I−(aq)] initial – [I3−(aq)]

The equilibrium constant (K) for the formation of the complex ion is then calculated with Eq (1). Actually the
equilibrium constant should be written in terms of the activities and the activity coefficients.
[I (aq)] 3−γI−

K = [I (aq)] [I (aq)] 2−γ γ3 I2 I− Equ 2

However, I− and I3−, with the same charge and in the same ionic environment, have very nearly the same activity
coefficient, which then tend to cancel out in Eq (2). Molecular iodine (I2) in both water and dichloromethane
behaves quite ideally, so its activity coefficient is very nearly unity.
NOTE: N-HEXANE WAS USED INSTEAD OF CARBON TETRECHLORIDE.
CHEMICALS AND APPARATUS
i. Beakers
ii. Separating funnel
iii. Solid iodine
iv. Clamp
v. 0.1M potassium iodide
vi. 0.05M sodium thiosulphate
vii. Starch indicator
viii. Distilled water
ix. Wash bottle
x. Hexane (organic solvent)
xi. Burette
xii. Volumetric flask

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AUGUSTINE ADU-KNUST
E-mail:adu.aug@gmail.com
 PROCEDURE

Weigh accurately 0.5g of iodine. Add it to 50cm3 of n-hexane in a separating funnel. 50cm3 of water is
added to the separating funnel and well shaken. Leave it to stand for some time for the phase to separate.
Run off the lower water layer into a container and the hexane layer is also run into a different container.
Take 25cm3 of the hexane layer into a conical flask. Add 25cm3 of 0.1M potassium iodide (KI) solution
and well shaken.
Titrate the mixture against 0.05M sodium thiosulphate solution using starch indicator.
Towards the end point of the titration the flask stoppered and well shaken after each addition of sodium
thiosulphate solution. The end point is reach when the n-hexane layer just becomes colourless.

Another 0.5g iodine is weighed and added to 50cm3 of n-hexane in a separating funnel.
Add 50cm3 of 0.10M potassium iodide (KI) solution and shake well. Leave it to stand for some time to
allow the phases to separate.
Run off the lower KI layer into a container and then the n-hexane into another container.
25cm3 of the hexane layer into a conical flask and add 25cm3 of 0.10M KI solution.
Titrate as before against 0.05M sodium thiosulphate solution.

EXPERIMENTAL DATA
1. Water + hexane against sodium thiosulphate

Burette readinga / cm3 I

Final rading 33.40
Initial reading 0.00
Titre value 33.40

2. KI + hexane against sodium thiosulphate

Burette readinga / cm3 I

Final rading 14.80
Initial reading 0.00
Titre value 14.80

pg. 4
AUGUSTINE ADU-KNUST
E-mail:adu.aug@gmail.com
The partition coefficient between water and hexane
Iodine reacts with thiosulphate in the ff. Way
I3- + 2 S2O32- ⇌ 3 I- + S4O62-
I2 + 2 S2O32- ⇌ 2 I- + S4O62-
I2 + I- ⇌ I3-
Mass of iodine = 0.5g, molar mass of iodine = 126.9 x 2 = 253.8g/mol
0.5𝑔
∴ 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐼 2 is given by 253.8𝑔/𝑚𝑜𝑙 = 1.97x10-3moles
𝑛[𝑆2 𝑂32− ] 2 1
=1 ⟹ 𝑛[𝐼2 ] = 2 𝑛[𝑆2 𝑂32− ]
𝑛[𝐼2 ]

𝑛[𝑆2 𝑂32− ] = 𝐶𝑜𝑛𝑐[𝑆2 𝑂32− ] × 𝑉𝑜𝑙[𝑆2 𝑂32− ]

= 0.05𝑀 × 0.0334𝑑𝑚3 = 1.67 × 10−3 𝑚𝑜𝑙
1
𝑛[𝐼2 ] = 2 × 1.67 × 10−3 𝑚
Number of moles of iodine in organic phase = 8.35 × 10−4 𝑚𝑜𝑙
=8.35×10−4 𝑚𝑜𝑙
Concentration of iodine in organic phase = = 0.0167 mol/dm3
0.05𝑑𝑚3
Number of moles in aqueous phase = initial moles of iodine – moles of iodine in organic phase
=1.97x10-3moles - 8.35 × 10−4 𝑚𝑜𝑙𝑒𝑠 = 1.135 𝑥 10−3 moles
1.135 𝑥 10−3 moles
Concentration in aqueous phase = = 0.0227M
0.05𝑑𝑚3

𝑐𝑜𝑛𝑐 𝑖𝑛 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑝ℎ𝑎𝑠𝑒 0.0167 𝑀

𝑝𝑎𝑟𝑡𝑖𝑡𝑖𝑜𝑛 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡, 𝐾𝐷 = = = 0.736
𝑐𝑜𝑛𝑐 𝑖𝑛 𝑎𝑞. 𝑝ℎ𝑎𝑠𝑒 0.0227𝑀

The formation constant for the tri-iodide ion formation

I2 + I- ⇌ I3-............... (I)
The formation constant is given by Ka
[𝐼3− ]
Ka of I3- = [𝐼 −]
2 ][𝐼
-
n(I2) = n(I3 )
m(I2) = 0.5g, M(I2) = 126.9 x 2 = 253.8gmol-1
0.5𝑔
∴ 𝑛(𝐼2 ) = = 1.97 × 10−3
253.8𝑔𝑚𝑜𝑙−1
At equilibrium, n(I3-) produced is the amount of I3- that reacted with the thiosulphate.
I3- + 2 S2O32- ⇌ 3 I- + S4O62-
1 1
𝑛(𝐼3− ) = 𝑛(𝑆2 𝑂32− ) = 0.05 × 14.8 × 10−3 = 3.7 × 10−4 𝑚𝑜𝑙𝑒𝑠
2 2
∴ 𝑛(𝐼3− ) 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = 3.7 × 10−4 𝑚𝑜𝑙𝑒𝑠
– 3.7×10−4 𝑚𝑜𝑙𝑒𝑠
[𝐼3 ] 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = = 7.4 × 10−3 𝑀
50×10−3
Initial conc. of I- is 0.1M
Mol of 𝐼 − = conc × 𝑣𝑜𝑙 = 0.1 × 0.05
= 5.0× 10-3𝑚𝑜𝑙

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AUGUSTINE ADU-KNUST
E-mail:adu.aug@gmail.com
𝑛(𝐼 − ) 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = 5 × 10−3 𝑚𝑜𝑙𝑒𝑠 − 3.7 × 10−4 𝑚𝑜𝑙𝑒𝑠
= 4.63 × 10−3 𝑚𝑜𝑙𝑒𝑠
𝑛 𝑎𝑡 𝑒𝑞𝑢. 4.63 × 10−3
[𝐼 − ]𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = =
𝑣 𝑎𝑡 𝑒𝑞𝑢. 50 × 10−3
= 0.0926𝑀
𝑛(𝐼2 ) 𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = 1.97 × 10−3 𝑚𝑜𝑙𝑒𝑠 − 3.7 × 10−4 𝑚𝑜𝑙𝑒𝑠
= 1.6 × 10−3 𝑚𝑜𝑙𝑒𝑠
𝑛 𝑎𝑡 𝑒𝑞𝑢. 1.6 × 10−4
[𝐼2 ]𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = =
𝑣 𝑎𝑡 𝑒𝑞𝑢. 50 × 10−3
= 0.0320𝑀
[𝐼3− ] 7.4×10−3
𝐾 = [𝐼 = (0.0320)(0.0926) = 2.50
2 ][𝐼 − ]

DISCUSSION.
The reaction between the thiosulphate and the iodine was a redox reaction with the I2 been
reduced and the thiosulphate being oxidized. In the dissolution of the solid iodine in the hexane,
it was noticed that the iodine did not completely dissolve but there was some remains in the solid
state. The concentration of the iodine in the organic phase was found to be smaller than that in
the aqueous phase.
The partition coefficient which was observed to be 0.736, which clearly shows that the I2
molecules clearly tend to quantitative distribution in the hexane; this implies that a large amount
of the solid iodine was extracted into the organic phase, the hexane.
In the second test, the iodide was reacted directly with the solid iodine in the hexane phase. This
was done in order to bring about extraction of most of the solid iodine into the KI solution phase.
The hexane layer that was drawn from the beaker was found to contain just some small amount
of the iodine. This was observed from the small volume of the thiosulphate that was obtained in
the titration. This implies that the amount of the iodine that reacted with the second addition of
the potassium iodide was very small showing that most of the initial iodine present was extracted
into the KI solution phase. Hence, the total tri-iodide ion concentration was the addition of the
iodide concentration in the KI solution and the one that reacted with the thiosulphate solution.

PRECAUTIONS
 There was vigorous shaking during the separation analysis in order to ensure higher
extraction.
 The separating solutions were allowed to stand without any interference to ensure higher
efficiency.
 During the draining, the funnel was opened bit by bit in order to ensure that pressure did
not build up in the funnel.
 In the second test, the titration was done in drop wise in order to avoid exceeding the
endpoint since just a small amount of the iodine was left in the hexane phase.

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AUGUSTINE ADU-KNUST
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  A little of the aqueous layer was left at the tip of the funnel in order to prevent some of
the organic phase from entering the aqueous phase that was collected.
ERROR ANALYSIS:
 Decomposition of Iodine molecule
 Indeterminate error
 PH and temperature as a factor
CONCLUSION
The partition coefficient was 0.736
The formation constant for the tri-iodide ion was found to be 2.50

REFERENCES

1. S. P. Mushtakova, G. V. Gerasimova, and T. M. Varlamova “Distribution of Iodine in

the
Systems Iodine–Water–Chloroform (Dichloromethane) and Iodine–Potassium Iodide–
Water–Chloroform (Dichloromethane)”, Journal of Analytical Chemistry 2009, 64,
125128.
2. General Chemistry Laboratories, University of Alberta;
http://www.chem.ualberta.ca/~ngee/Expt.N_05.html
3. G. Jones, and B.B. Kaplan, “THE IODIDE, IODINE, TRI-IODIDE EQUILIBRIUM
AND THE FREE ENERGY OF FORMATION OF SILVER IODIDE”, J. Amer. Chem.,
1928, 50, 1845-1864.
4. H.M. Dawson, “On the nature of polyiodides and their dissociation in aqueous solution”,
J. Chem. Soc. 1901, 79, 238-247.

5. http://en.wikipedia.org/wiki/Chemical_equilibrium
6. http://www.answers.com/topic/partition-coefficient

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