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CH 102 Experiment #5

Aldehydes and Ketones


Objectives:
Observe the reactions of aldehydes and
ketones
Identify three unknown chemicals as
aldehydes, methyl ketones, or neither.

BACKGROUND
The major similarity between an aldehyde and
a ketone is the carbonyl group. A carbonyl
group is a carbon atom doubly bonded to an
oxygen atom, as depicted below.

..O..
C

Both molecules have a carbonyl group, the


aldehyde and ketone differ in what atom is
bonded to the carbonyl carbon. The carbonyl
carbon of an aldehyde is bonded to two
hydrogens or one hydrogen and one carbon
(the end). The carbonyl carbon of a ketone is
bonded to two carbons (in the middle).

..O..

..O..

R C H
Aldehyde

R C R'
Ketone

Remember that the R symbolizes any carbon


side-chain, from one carbon to a million
carbons. The carbonyl group of an aldehyde is
on the terminal (last) carbon and the carbonyl
group of the ketone is not.
Where are aldehydes and ketones found?
Sugars, flavors, steroids, intermediates in
biological chemical production.
Physical Properties
IMF forces: The only intermolecular forces
are Dipolar and LDF. The double connection
makes the CO double bond even larger dipole
than a CO single bond and therefore exerts a
more attractive force than ethers.
Solubility: Aldehydes and ketones cannot
give an H-bond but they can receive two Hbond from water (the carbonyl has 2 lone
pairs). Since they have a larger dipole (which
means the oxygen is more negative) than
alcohols, water will form a stronger H-bond to
them. This balances out to make the
aldehydes and ketones to have about the same
solubility in water as a similar sized alcohol.

Melting point/boiling point: Since they


cannot give an H-bond the only forces that
hold the molecules of the pure substance
together is dipole-dipole attractions and LDF
attractions. A carbonyl is more polar than an
ether connection so we expect the melting
and boiling point for similar sized aldehydes
and ketones to be higher than ethers and
lower than alcohols
Acidity: Aldehydes and ketones are neutral.
Physical Tests
We will not be performing any physical tests
today like solubility
Chemical Properties
Flammability: All aldehydes and ketones
are flammable. The lower molecular weight
ones which have a lower boiling point will be
more volatile (evaporate more) and therefore
have the potential for flashing or explosion
(rapid oxidation) due being premixed with
oxygen in the air. Liquids and solids only
burn at the surface and are limited by the
amount of oxygen that gets to them. Gases
mixed with oxygen can burn all at once.
Oxidation [O]: Aldehydes can be oxidized,
[O], to carboxylic acids. Ketones are not
easily oxidized. This is one way to distinguish
between the aldehyde and the ketone. We will
be using Bordwells reagent (chromic acid)
and Tollens reagent (ammonia/silver ion) as
oxidizing agents. Addition of an oxidizing
reagent will only show a change with
aldehydes.
Addition Reactions: Aldehydes and ketones
can undergo addition reactions. An addition
reaction is where a whole molecule is added
across the double bond and it becomes a
single bond.
Reduction [H] (the addition of H 2): This
type of addition reaction is where H2 is added
to the carbonyl to give the corresponding
alcohol. Aldehydes can be reduced, [H],
back to primary alcohols and ketones can be
reduced to secondary alcohols by the addition
of H2 and a catalyst. The next figure
summarizes the oxidation and reduction
reactions.
O H
R C

[O]

R C
[H]

[O]

R C O H

aldehyde

[H]
carboxylic acid

primary alcohol

O H
R C
H

[O]

O
R C

[H]

[O]

N.R.

ketone

[H]

secondary alcohol

Lab 5 Aldehydes and Ketones

Addition of alcohol (Ketal, acetal).


Aldehydes and ketones can both react with
alcohols (usually under acid conditions) to form
an addition product. Any alcohol should react
but usually the alcohols chosen are small like
methanol or ethanol. Aldehydes add the first
alcohol to become a hemi-acetal and then add
a second alcohol to form a stable acetal and
release water. Ketones add the first alcohol to
become a hemi-ketal and then add a second
alcohol to form a stable ketal and release
water.
OH

O
R C H

H+ and
R'-OH

R C R'

H+ and
R''-OH

OH

OR"

OR"

hemiketal
(intermediate)

ketal

alcohol

ketone

H2O

OR"
R C R'

R C R'

R" O H

H2O

acetal

hemiacetal

OR'

OR'

alcohol

aldehyde

OR'
R C H

R C H

R' O H

The Tollens Test. This will test only for


aldehydes. The Tollens reagent, composed of
a silver-ammonium ion, will form solid silver
as it oxidizes that aldehyde. This silver will
plate a glass surface creating a mirror.
O
R

C H

2 Ag(NH3)2OH

aldehyde

O
2 Ag (s)

H2O

3 NH3

black ppt or
silver mirror

The Iodiform Test. This will test specifically


for methyl ketones by giving a yellow
precipitate. It should be noted that aldehydes
can also add the reagent but will form a white
precipitate (ppt), and it does not test for
ketones in general.
O
R

C CH3

+ 3 I2 +

4 NaOH

alpha
methyl
ketone

O
R

+ 3 NaI +

C
O Na

3 H2O

CHI3 (s)
yellow

Chemical Tests
Five tests will be used in this experiment.
1. Iodoform test
2. Bordwell test (Chromic acid test)
3. Tollens test
4. 2,4-DNP test
5. Purpald test
Both chromic acid and Tollens reagent are
used to differentiate between aldehydes and
ketones. Aldehydes are oxidized relatively
easily, while ketones are not easily oxidized.
Chromic acid Test (Bordwells Reagent or
Jones reagent)
The chromic acid (CrO3) will change in color
from orange to brown to green/blue when it
oxidizes an aldehyde. It should stay an orange
solution if it is not. Note: A negative result of
this test will not tell you if you have a ketone,
it only tells you that you do not have an
aldehyde.

The 2,4-DNP Test:


2,4-DNP (2,4-dinitrophenylhydrazine)
This chemical will add to only carbonyls of
aldehydes and ketones and not carboxylic
acids or esters. When the product is formed it
will be a yellow or orange or red solid (ppt).
Other chemicals will not react and therefore
will leave a clear (but orange colored)
solution with no solids.
R1
N

NH2

NH

NH

O
C
R1

H2SO4

O2N

NO2
2,4-DNP

R2

alcohol

R2

aldehyde
or ketone

O2N

H2O

NO2
red ppt

O
3R

C H

aldehyde

2 CrO3

3 H2SO4

orange
O
3 R

C OH

carboxylic
acid

Lab 5 Aldehydes and Ketones

3H2O

Cr2(SO4)3
green

Purpald Test: (4-amino-3-hydrazino-5mercapto-1,2,4-triazole)


Like the Tollens reaction, this reaction will only
react with aldehydes and its product is easily
biodegradable. The reaction is rather fast for
the first step, but it takes time for O2 from the
air to remove the last hydrogens and let the
product form a second conjugated ring that
makes it the purple color.
R

O
R CH
aldehyde

HS

NH2

NH2

NH

C
O2 (air)

HS

Purpald
(colorless?)

Lab 5 Aldehydes and Ketones

purple color

3 H2O

Of Medical Interest: Ketosis.


Ketones are a normal byproduct of fat
metabolism (the breaking down of fat into
energy). Normally, your body is efficient at
removing these, but when certain enzymes are
absent or damaged, the concentration of ketones
in the body can build up to dangerous levels.
This can also lower the pH of the blood, hence
the origin of the term ketoacidosis.
Certain individuals are predisposed towards
ketosis. For example, those with diabetes have
low insulin levels and can not process glucose
(sugar) for energy. Therefore, their bodies break
down fat, leading to a rise in ketone levels.
Popular low-carbohydrate diets (such as Atkins)
encourage the breakdown of fat and can induce
so-called dietary ketosis.
Ketones can be excreted through the urine and
those that are volatile (such as acetone) can be
expelled through the lungs. Diabetics can be
mistaken for being drunk by the odor on their
breath, and acetone being expelled through the
lungs can give a false positive result on early
model breathalyzers. However, don't expect to
escape a ticket as driving while impaired (due to
low blood sugar) is still a traffic offense whether
you are drunk or not.
Severe cases of ketosis can lead to coma and
death if untreated.

EXPERIMENTAL PROCEDURE
CAUTION! Chromic acid is very corrosive and
any spills should be immediately flushed with
water. Use gloves with these reagents.
Dispose of reaction mixtures and excess
reagents in waste containers only as directed
by this handout or your instructor.
1. Your observations are the most important
aspect of this lab. Remember to be as
descriptive as possible and highly organized.
Carefully record all observations in the data
tables. For each test you will use 5 tubes:
Tube 1 butanal
Tube 2 acetone
Tube 3 unk A
Tube 4 unk B
Tube 5 unk C
Test 1, Iodoform Test
2. Take 5 test tubes. In tube 1 add 5 drops of
butanal, tube 2: 5 drops of acetone, tube
3: 5 drops unk A, tube 4: 5 drops unk B,
and in tube 5: 5 drops of unk C.
3. Add 1 mL of H2O to each tube.
4. To each test tube, add 0.5 mL of 10% NaOH
(which may be labeled as 3M NaOH).
5. Add 10 drops of the I2-KI test reagent (may
be labeled Iodoform) while shaking.
6. Examine the tubes for a yellow (not white)
precipitate (ppt). Set them aside and
examine them again after youve
completed the other tests; formation of the
precipitate can be slow.
7. At the end of the period, discard the waste
in the organic waste container. Rinse with a
small amount of acetone, and place the
rinse in the halogenated waste container.
Then wash the test tubes with soap and
water.
Test 2, Chromic Acid (Jones Reagent))
8. Use 5 clean test tubes. In tube 1: add 5
drops of butanal, tube 2: 5 drops acetone,
etc. (as before in step 2))
9. To each test tube add 3 drops of Chromic
Acid Reagent (Jones Reagent or Bordwells
Reagent) and agitate (by flicking the tube
with your finger). Note any color changes
and note any temperature changes.
10. Discard all waste in the chromium/organic
waste container. Rinse your test tubes with
a little acetone and discard the rinse in the
chromium/organic waste container. Then
wash the tubes with soap and water.

Lab 5 Aldehydes and Ketones

Test 3, Tollens test


11. Take 5 disposable test tubes and rinse
them with some sodium hydroxide (NaOH)
solution. The rinse can be put directly
down the sink and its OK to leave a few
drops behind.
12. To each rinsed test tubes add 12 drops of
Tollens reagent.
13. Add 5 drops of butanal to the first tube
(1) and agitate (mix) by flicking the tube
to mix thoroughly. Look for a silver
mirror forming or a black precipiitate
14. repeat step 13 in tubes 2-5 as before with
acetone (2), unk A (3), unk B (4), unk C
(5).
15. Discard all waste in the silver/organic
waste container. Rinse your test tubes
with a little acetone and discard the rinse
in the Silver/Organic Waste container.
Remove the labels and place test tubes in
the dirty test tube box.
Test 4, DNP test (for aldehydes and ketones)
16.In test tube 1 add five drops of butanal, in
2, add 5 drops acetone, etc. (see step 2)
17. To each of those test tubes add 10 drops
of DNP reagent and flick the tubes to get
mixing.
18. Examine each test tube for the formation
of a ppt that may be yellow or orange or
red. No ppt (solids) will be a negative
result.
19. Discard all waste in the general organic
waste.
Test 5, Purpald test (for aldehydes)
20. In test tube 1 add 5 drops of butanal, to
tube 2, add 5 drops of acetone, etc..
21. Add 2 drops of Purpald Reagent and
agitate by flicking the tube to mix
thoroughly. Keep mixing the tubes for a
few minutes as the reaction takes place
when oxygen in the air finalizes the
reaction. A positive test a purple colored
solids.
22. Discard all waste in the General Organic
Waste
23. Using all the data you have just collected,
identify the unknowns as an aldehyde, a
methyl ketone or neither.

Lab Report:
Pre-lab
On a separate paper write your title, purpose
and name
During lab
Fill in your data table.
Use the models to make the acetals and ketals
on the acetals and ketals worksheet at the
back of the lab.
Post-lab
(You can start your analysis on the front of the
title page)
Analysis: Explain how you identified each of
your unknowns as either an aldehyde, a
methyl ketone, or neither. Be specific,
explaining the purpose of a negative test as
well as a positive test.
Draw the structures forany two aldehydes and
any two two ketones and name each.
Discussion: Restate the identities of your
unknowns. Explain the utility of each test.

Lab 5 Aldehydes and Ketones

Purposely left blank

Lab 5 Aldehydes and Ketones

Name__________________________

Lab 5 Data sheet: Aldehydes and Ketones


Chemical Properties
Note: the term ppt is a standard abbreviation for precipitate which means
solids formed in the reaction
1. Iodoform ( Lucas Reagent)
Tests for: alpha-methyl ketones
Compound
Observations

Positive Test: milky yellow ppt


2. Chromic Acid Test ( Bordwells Reagent)
Tests for: aldehydes (and 1 and 2 alcohols)
Compound
Observations

Fails for: aldehydes , alcohols

Negative Test: stays clear or milky white

Fails for: ketones and tertiary alcohols

Positive Test: turns brown then blue/green ppt


Negative Test stays orange
Note: If not enough chromic acid reagent is added it may stay brown. If you are not sure then add
another one or two drops of reagent and agitate again.
3. Tollens Test ( Silver ion in ammonia))
Tests for: aldehydes
Compound
Observations

Fails for: ketones and tertiary alcohols

Positive Test: gives black ppt or cool silver mirror


Negative Test: stays colorless (see note)
Note: Sometimes the Tollens reagent as it gets old will have some black ppt in it.

Lab 5 Aldehydes and Ketones

4. 2,4-DNP Test
Tests for: aldehydes and ketones
Compound
Observations

Positive Test: gives yellow/orange/red ppt


3. Purpald Test
Tests for: aldehydes
Compound

Fails for: alcohols carboxylic acids and esters

Negative Test: stays orange but clear.


Fails for: ketones, alcohols, acids and esters

Observations

Positive Test: gives purple color after exposure to air.

Lab 5 Aldehydes and Ketones

Negative Test: stays colorless (see note)

Models and Structures of Acetals and Ketals


Use the molecular models to
Make a model of Butanal and make models of two individual methanols.
Draw them
Note: you are just drawing the starting molecules, not the reaction. (step 1 & 2 next page)

Draw the initial butanal and one methanol you did above then combine the models to form the
hemiacetal .
Draw the reaction below and the picture of the model above. (step 3 next page)

Start with the hemiacetal you drew above and then draw the second alcohol then combine them together
to form the full acetal and show the water released. Draw the reaction below and the picture of the
model above. (step 4 next page)

As above make a model of 2-butanone and two individual methanols.

React the ketone with one methanol to make the hemiketal.

Draw it (step 1&2 next page)

Draw it (step 3 next page)

Start with the hemiketal and react it with a second alcohol to make the full ketal and show water
released.
Draw it (step 4 next page)

Lab 5 Aldehydes and Ketones

OK, Here is the step by step on how to do the previous page:


1. Start by building the model of the starting aledehyde (butanal) or the starting ketone (2butanone). You should have a molecule which has a red oxygen double connected to a black
carbon (a carbonyl)
2. Make the two alcohols which will be added later (methanol) and draw them
3. Now for the first reaction:
a) Pull out one of the bonds from the C=O from the carbon side (this will leave a bond hanging
on the red oxygen and a hole on the carbon.
b) Pull the white H-ball off from the OH on the methanol this will leave a white ball with a hole
and the oxygen with a bond hanging off of it.
c) Now the tricky part. Put the dangling bond of the methanol into the hole of the carbon of the
carbonyl and put the white hydrogen on the dangling oxygen of the carbonyl.
d) You now have the hemi product.
Break here
(at C)

Break here
(at H)

O
R

C H

aldehyde

H O R"

O H

C H

first
alcohol

R C H

R"

O R"
hemi-acetal

=hole

4. Now for the second reaction:


a) Pull out the second bond to the red oxygen from the original carbon that was the carbonyl.
This will leave a hole at the carbon and the OH is separated from the molecule with a
dangling bond.
b) Pull the white H-ball off from the OH on the second methanol this will leave a white ball with
a hole and the oxygen with a bond hanging off of it.
c) Now the tricky part (again). Put the dangling bond of the methanol into the hole of the carbon
of the hemi product and put the white hydrogen on the dangling bond of the isolated OH.
d) You now have the full acetal (or ketal).
Break here
(at H)

Break here
(at C)

O H

O H
H

O H
R C H
O R"
hemi-acetal

H O R"
second
alcohol

C H
O R"

R"

O R"
R C H

=hole

O R"
acetal

In the bottom half of the paper you will repeat this procedure with 2-butanone first to form the hemi
ketal with the first alcohol. Then starting with the hemiketal you will form the full ketal using the
second alcohol.

Lab 5 Aldehydes and Ketones

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