Experiment No.

7

The Iodoform Reaction

I. Objectives

At the end oI this activity, we should be able to (1) identiIy the organic compounds that
will give a positive test and as well those organic compounds that will give a negative test using
iodoIorm reaction. (2) Also to identiIy the reason why such organic compounds give a positive
test to iodoIorm reaction. (3) And to identiIy the reason why such organic compounds give a
negative test to iodoIorm reaction.

II. Materials
-Vials (6) -Droppers (8) -Organic compounds

III. Procedure (Three trials)





15 drops oI 1 M NaOH





25 drops oI KI-I2







Prepare 6 vials.
Place 5 drops oI each organic
compounds in each oI the
vials. vial compound
Put 15 drops oI 1 M NaOH to
each oI the vials.
Add 25 drops oI KI-I2 to
each oI the vials.
Wait Ior another 5-10
minutes. Observe.
Shake. Wait Ior 2-3 minutes.
Observe.
Shake. Observe.
1 2 3 4 5 6
1 2 3 4 5 6
1 2 3 4 5 6
Ethanol N-butanol Tert-butyl Iso-butyl Formalin Acetone
1 2 3 4 5 6
IV. Data and Results

15 drops of NaOH + 25 drops of KI-I2
Organic Compound T1 T2 T3
Ethanol
Very cloudy or turbid;
pale yellow
precipitate Iormed at
the bottom oI the vial
Cloudy or turbid; pale
yellow precipitate
Iormed at the bottom
oI the vial
Cloudy or turbid; pale
yellow precipitate
Iormed at the bottom
oI the vial
N- butanol
the solution was oily;
very cloudy or turbid;
pale yellow
precipitate Iormed at
the bottom oI the vial
the solution was oily;
cloudy or turbid; pale
yellow precipitate
Iormed at the bottom
oI the vial
the solution was oily;
very cloudy or turbid;
pale yellow
precipitate Iormed at
the bottom oI the vial
Tert-butyl No changed No changed No changed
Iso-butyl
Cloudy or turbid; pale
yellow precipitate
Iormed at the bottom
oI the vial
Very cloudy or turbid;
pale yellow
precipitate Iormed at
the bottom oI the vial
Very cloudy or turbid;
pale yellow
precipitate Iormed at
the bottom oI the vial
Formaldehyde No changed No changed No changed
Propanone
Pale yellow
precipitate Iormed at
the bottom oI the vial;
it is very turbid or
cloudy
Pale yellow
precipitate Iormed at
the bottom oI the vial;
it is very turbid or
cloudy
Pale yellow
precipitate Iormed at
the bottom oI the vial;
it is very turbid or
cloudy


Organic Compound Smell
Ethanol It has a bad odor
N-butanol Smell like hospital/s
Ter-butyl Smell like acetone
Iso-butyl Smell like hospital/s
Formaldehyde It has a bad odor
Propanone Smell like hospital/s

V. Discussions or Questions
"1. What do you observe aIter 2-3 and aIter 5-10 minutes? Prepare a table like the one below.
TABLE 1: TESTING OF VARIOUS COMPOUNDS WITH HYPOIODITE (I2/KI -
NaOH) SOLUTION
COMPOUND
APPEARANCE OF WELL
CONTENTS AFTER 2 TO 3
MINUTES
PRECIPITATE (CHI3(s))
FORMATION? (After 5-10
minutes)
Ethanol Turbid/ Cloudy Precipitate was Iormed
N-butanol Turbid/ Cloudy; Oily Precipitate was Iormed
Tert-butyl No changed No changed
Iso-butyl Turbid/ Cloudy Precipitate was Iormed
Formaldehyde No changed No changed
Propanone Turbid/ Cloudy Precipitate was Iormed

"2. What do you notice in the vials where turbidity was observed earlier?
O We`ve noticed that aIter 3-5 minutes the solution became cloudy or turbid and aIter 5-10
minutes there was precipitate Iorming at the bottom oI the vial.
"3a. What do you see?
O We saw precipitate Iorming at the bottom oI the vials.

"3b. What do you notice?
O We`ve noticed that the color oI the precipitate Iormed was pale yellow. And when we
leave it, the precipitate will settle at the bottom oI the vial and also iI we do not shake it
well they will not be dispersed or be carried.

"4. Describe the odour/ smell.
O The smell was like the smell oI the hospitals.

"5. Examine the structures oI propanone and cyclohexanone along side. What is the diIIerence
in structure between these two ketones, besides the Iact that one ketone is cyclic and the other
aliphatic?

Propanone has CH3 attached to CO

Cyclohexanone has CH2 attached to CO

O It is easier Ior propanone to bond with other compounds than cyclohexanone because oI
its structure.
"6. Based upon your answer to question 1 and the observations made in this experiment, how
does the iodoIorm test help to distinguish methyl ketones Irom non-methyl ketones?
O Methyl ketones can be distinguished Irom non- methyl ketones by their reaction with
iodine in a basic solution to yield iodoIorm (CHI3) as a pale yellow colored precipitate.

". The reaction oI a methyl ketone with iodine solution in the presence oI aqueous sodium
hydroxide is
shown in the equation below:
RCOCH3(l) + 3I2(aq) + 4NaOH(aq) RCOONa(aq) + CHI3(s) + 3NaI(aq) +
3H2O(l)
(where R H, alkyl or aryl group)
i. Which part oI the ketone molecule has been involved in the Iormation oI an iodoIorm
molecule?
O The part oI the ketone molecule has been involved in the Iormation oI an iodoIorm
molecule is the CH3 molecule.
ii. Use your answer to i to explain why cyclohexanone gives a negative reaction in the iodoIorm
test.
O Cyclohexanone gives a negative reaction in iodoIorm test because it doesn`t have methyl
group that will undergo in reaction.

"8. Formaldehyde gives a negative result in the iodoIorm test. Do you think that the iodoIorm
test could be used to distinguish methyl ketones Irom all aldehydes? Explain your answer with
reIerence to the equation given in question 3.
O I don`t think that iodoIorm test could be used to distinguish methyl ketones Irom all
aldehydes because ethanal is an alddehyde that gives a positive test to iodoIorm test.



"R" can be a hydrogen atom or a hydrocarbon group (Ior example, an alkyl group).
II "R" is hydrogen, then you have the aldehyde ethanal, CH
3
CHO.
Ethanal is the only aldehyde to give the triiodomethane (iodoIorm) reaction
O At this point ethanal can give a positive test to iodoIorm test because it has what is
needed in the reaction.
". The equation Ior the initial reaction between an alcohol (primary or secondary) and iodine
solution in the presence oI aqueous sodium hydroxide is:
RCH(OH)R.(l) + I2(aq) + 2NaOH(aq) RCOR.(aq) + 2NaI(aq) + 2H2O(l)
where R and R. H, alkyl or aryl group
i. According to the equation, which alcohols should react with the hypoiodite solution?
O The iodoIorm reaction is given by compounds with a methyl group next to a carbonyl
group. Secondary alcohols with a CH
3
on the carbon carrying the OH (eg propan-2-ol)
that can be oxidized to carbonyl compounds oI this type, also give a positive iodoIorm
test.
O Ethanol is the only primary alcohol which will give a positive test.

The Iull mechanism Ior the second and third steps are:
$econd step

This occurs three times to give CI
3
CHO
Third step

The negative charge on the carbon in the I
3
C

ion is stabilised by the three electronegative iodine

atoms.

ii. Use the equation to explain why certain alcohols are able to give a positive iodoIorm reaction.
O Certain alcohols are able to give a positive iodoIorm reaction because they have CH
3
on
the carbon carrying the OH.

iii. Why does ethanol give a positive iodoIorm test but methanol does not? (Hint. look at the
reaction equation)
O Ethanol gave a positive test but methanol doesn`t because methanol does not have any H,
alkyl or aryl group attached to CH3.

"10. ReIer back to Table 1. Write down the reactions taking place Ior those ketones and alcohols
which gave a positive iodoIorm test.

For ethanol:


For secondary alcohols with an adjacent methyl group:.

For Ketone:


"11. You are working in a company laboratory. You have been asked to use 1-propanol in a
particular experiment. You Iind a cupboard in which there is a shelI Ior alcohols, but the bottles
are not labelled. You know that ethanol and 1-propanol are used oIten. Explain how you will use
the iodoIorm test to locate a bottle oI 1-propanol in the presence oI bottles oI ethanol. Predict the
outcome oI your investigation and reIer to the structures oI the alcohol compounds when
necessary.
O Using iodoIorm test, ethanol will be more cloudy or turbid than 1-propanol.
VI. Conclusion
We thereIore conclude that at the end oI this activity, we have identiIied the organic
compounds that gave a positive test and as well those organic compounds that gave a negative
test using iodoIorm reaction. The organic compounds that gave a positive test are ethanol, n-
butanol, iso-butyl and propanone while the organic compounds that gave a negative test are tert-
butyl and Iormaldehyde.
The reason why such compounds gave a positive test is because they contain CH3-CO
group in molecule that will undergo in the reaction. The group to which the CH
3
-CO group is
attached can be aryl, alkyl and hydrogen. And the reason why such compounds gave a negative
test is because they do not contain CH3-CO group in molecule that will undergo in the reaction
and they gave a negative test because R group is a di-ortho substituted aryl group. A positive test
is seen when the solution became turbid and a pale yellow precipitate Iormed at the bottom oI the
vial and they smell like hospital. The precipitate is called iodoIorm. A negative test is seen when
the solution doesn`t have any changes.
The iodoIorm reaction is characteristic Ior methylketones as well as Ior alcohols (e.g.
ethanol, 2-propanol), that can be oxidized to a methyl carbonyl compounds. The iodoIorm test is
a test Ior the existence oI the CH3-CO group in a molecule. The group to which the CH3-CO
group is attached can be aryl, alkyl and hydrogen.
Both ethanol and 2-propanol are oxidized by iodine to give ethanale or acetone. (1).

When a-methyl carbonyl compounds react with iodine in the presence oI a base, the hydrogen
atoms on the carbon adjacent to the carbonyl group (a hydrogens) are subsituted by iodine to
Iorm tri iodo methyl carbonyl compounds which react with OH - to produce iodoIorm and
carboxylic acid (2):

Reaction mechanism:
The hydrogen atoms on the methyl group are slightly acidic and can be removed with hydroxide.
The carbanion Iormed then react with iodine molecules to give a iodide ion and a monoiodonated
methyl carbonyl derivate. Introduction oI the Iirst iodine atom (owing to its electronegativity)
makes the remaining hydrogens oI the methyl group more acidic. Hence a base-catalized
iodination oI a monohalogenated methyl carbonyl derivate occurs at the carbon that is already
substituted. Finally a tri iodo methyl carbonyl derivate is Iormed.

The next step is a nucleophilic attack by hydroxide on the carbonyl carbon atom. A carbon-
carbon bond cleavage occurs and a triiodomethanide ion departs. The triiodomethanide ion is
unusually stable. Its negative charge is dispersed by the three negative iodine atoms. In the last
step a proton transIer takes place between carboxylic acid and triiodomethanide ion to Iorm
ultimately carboxylate ion and iodoIorm.