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PROJECT 10
Multiple Oxidation States
INTRODUCTION:
Many of the non-metal main group elements, like the transition-metals, exhibit multiple
oxidation states. If one looks at the groups there is a definite trend towards the stability of lower
oxidation states for elements further down the groups (the primary oxidation number decreasing
by two). It should be noted that oxidation state in this context does not refer to ionic charges
on the elements. Remember that compounds of the main group non-metals are primarily
covalent. For example for the Group 14 (IVA) elements we find that carbon, silicon, and
germanium are nearly always found in the IV oxidation state. Tin is equally found in either the II
or IV oxidation state, whereas lead is most often found in the II oxidation state, with the IV state
being fairly unstable.
The trend can be rationalized by considering the valence electron configuration of the
elements with respect to oxidation states.1 Let’s look again at Group 14 (IVA) and the valence
electron configurations for each oxidation state:

Oxidation state II is achieved if the element retains its expected, neutral, valance electron
configuration. To achieve oxidation state IV a valence electron of the neutral element must be
promoted from the ns orbital to the np orbital. To decide how feasible this is, there are two
considerations:
• The energy required to promote the electron (this becomes smaller for elements further
down the group as valence electrons are further from the nucleus).
• The energy gained through the strength of the bonds formed (this decreases for elements
further down the group as orbitals get bigger and, therefore, orbital overlap to form bonds
becomes poorer).

1
Oxidation state signifies the number of charges an atom would have in a molecule if shared electrons were transferred
completely to the more electronegative atom, so can be related to the number of unpaired electrons for an atom.
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For lead the cost of promoting an electron must be higher than the energy gained through the
formation of two more bonds. The two electrons in the ns orbital, therefore, do no become involved
in bonding and are known as an “inert pair”. For carbon, silicon, and germanium the cost of
electron promotion must be more than compensated for by the formation of two more bonds. For
tin the cost and return must be of equal magnitude such that both oxidation states have similar
chances of occurring.

In this experiment you will synthesize tin(IV) and tin(II) iodide. Tin(IV) iodide is formed
by heating metallic tin in the presence of iodine. Tin(II) iodide is formed by reaction of metallic
tin with concentrated hydrochloric acid to first form tin(II) chloride, which then undergoes an ion
exchange with a solution of zinc iodide.2

PRE-LAB ASSIGNMENTS:
Based on the procedures, outline the reactions that will occur as you synthesize tin(IV) and
tin(II) iodide. To help you, read Experiment 9 of “Microscale Inorganic Chemistry - A
Comprehensive Laboratory Experience” by Zvi Szafran, Ronald M. Pike and Mono M. Singh.
Wiley, 1991.
Consult the MSDS sheets found in the laboratory. Record in your lab note-book the
precautions you have to take when handling Sn(s), Zn(s), CH2Cl2, HCl and I2.
You will not be allowed to start the project until you have shown your work to your TA.

2
The ion exchange between solutions is known as a metathesis or double decomposition reaction.
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PROCEDURE: (Work in pairs)

A. Preparation of tin(IV) iodide (stannic iodide)

Add 0.30 g (2.5 mmol) of tin and 1.2 g (4.7 mmol) of iodine to a 50 mL Erlenmeyer flask
along with a small magnetic stirring bar. In a fume hood, add 5 mL of toluene and gently heat and
stir the solution on a hot plate until the toluene just begins to boil. Reduce the heat and continue to
gently heat and stir the solution for a further 30 minutes until it has changed colour from violet to
orange-brown.

Filter the hot solution through Pasteur filter pipet with a glass wool plug into a second 50
mL Erlenmeyer flask to remove unreacted tin, then cool the filtrate solution in an ice-water bath.
Collect the orange crystals of tin(IV) iodide by vacuum filtration using a Hirsch funnel and wash
the crystals with 2 mL of cold toluene. Transfer the crystals into a fresh 50 mL Erlenmeyer flask and
re-dissolve them in a minimum amount of hot toluene (~1-2 mL). Cool the solution in an ice bath to
recrystallize the product, then collect the crystals using a Hirsh funnel and dry them on a piece of filter
paper. Determine the melting point of the product, and calculate a percentage yield.

Check the success of your synthesis:

• Dissolve a small amount of your product in 5 mL of acetone. Divide this into two portions,
A and B. To portion A, add a few drops of water. To portion B, add a few drops of saturated
KI solution. Observe what happens in each case, and explain your observations in terms of
the nature of the product.

B. Preparation of tin(II) iodide (stannous iodide)

NOTE: This reaction generates hydrogen gas, which forms explosive mixtures with
air. Open flames must not be used in this experiment.

Cut a sample of tin foil weighing 160 mg (1.36 mmol) into smaller pieces, and place them
into a 10 mL beaker along with a small stir bar. Add 1 mL of concentrated HCl and 2 - 3
drops of 0.1 M CuSO4 solution. Place the beaker on a hot plate, cover it with a watch glass,
and with stirring heat the mixture to just below boiling. Note the evolution of H2 gas in the
flask. While the reaction between the tin and HCl is underway, proceed to the next step of the
synthesis.

In another 10 mL beaker, place 100 mg (1.53 mmol) of granular zinc and 1 mL of RO

water along with a stir bar. Add 300 mg (1.20 mmol) of iodine crystals to the beaker and then
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cover it with a watch glass and gently heat and stir the mixture. The reaction of iodine
with zinc is slow, but the brown color of dissolved iodine will gradually fade to a light yellow
as the reaction progresses towards completion (~30-45 minutes). Some unreacted zinc remains
at this point.

Transfer the ZnI2 solution from the beaker to another 10 mL beaker using a Pasteur filter
pipet. The filtered solution should be clear, having no suspension of metallic zinc. To ensure
complete removal of ZnI2, rinse the contents of the beaker with a few drops of RO water,
and transfer the washings using the same filter pipet to the beaker (do not use too much water
to rinse the zinc residue; dilution will reduce the yield of product).

Check the tin-HCl mixture. If some metallic tin still remains unreacted, add a few more
drops of concentrated HCl and warm the mixture on the hot plate (At the end of the reaction some
black suspended particles will remain - this is normal). Filter the tin solution through a clean
Pasteur filter pipet and transfer it dropwise directly to the beaker containing the ZnI2 solution.
As soon as the SnCl2 solution comes into contact with the ZnI2 solution an orange-yellow
precipitate of SnI2 will form. Complete precipitation by cooling the solution in an ice bath.
Collect the solid by vacuum filtration using a Hirsch funnel.

Transfer the crude SnI2 from the Hirsch funnel to the same beaker in which the precipitation
was carried out. Add 2-3 drops of concentrated HCl and gently heat to dissolve the solid. Cool
the beaker to room temperature and continue to cool it in an ice bath to complete the
recrystallization. Collect the product by suction filtration on a Hirsch funnel and allow it to dry.

Check the success of your synthesis:

• Weigh the product and calculate the percentage yield. Obtain the melting point.

REFERENCE (text on reserve for Chem 331):

“Microscale Inorganic Chemistry - A Comprehensive Laboratory Experience” by Zvi Szafran,
Ronald M. Pike and Mono M. Singh. Wiley, 1991. This project is based on Experiment 9. This
reference will lead you to the primary reference!!

AS PART OF YOUR INTRODUCTION AND/OR DISCUSSION YOU SHOULD

ADDRESS THE FOLLOWING:
1. Write all relevant oxidation and reduction half-reactions for this experiment.
2. While SnI4 is quite stable, PbI4 does not exist as a stable compound; explain.
3. It was observed that SnI4 is soluble in acetone. What does this tell you about the ionic
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nature of this compound? What is the charge on the tin atom? What was the effect of
adding KI to the acetone solution?
4. When heating metallic tin in the presence of iodine, only SnI4 is formed, no SnI2. Explain
this experimental result.