College of Science

Determination of Ethanol Concentration in Aqueous Solutions

Safety The amount of unreacted dichromate is then

determined by adding potassium iodide solution which
is also oxidised by the potassium dichromate forming
Lab coats, safety glasses and enclosed footwear must iodine.
be worn at all times in the laboratory.
Determination of Ethanol Concentration
The acid dichromate solution needs to be prepared Cr2O72−in+ 14 H+ + 6 I− → 2 Cr3+ + 3 I2 + 7 H2O
Aqueous
with care. Any concentrated Solutions acid spills must be cleaned The iodine is then titrated with a standard solution of
up by very carefully diluting with water before wiping sodium thiosulfate and the titration results are used to
up. Take care to put the water in the flask first before calculate the ethanol content of the original solution.
adding the acid, and add the acid slowly with constant
Introduction a flask and the alcoholic beverage sample is suspended
swirling.This
The flaskuses
method will gettitration
a redox quitetohot.find the 2 S2O3water
in a small container above it (see diagram).The 2−
+ I → S4O62− + 2 I−
and ethanol slowly evaporate and as the ethanol comes2
concentration of ethanol in an aqueous solution. The
ethanol is oxidised to ethanoic acid by reacting it with
in contact with the Because
dichromatealcoholic beverages
it first dissolves, and is such as wine or beer
then oxidised. More ethanol evaporates until eventually
Introduction 2− +
an excess of potassium dichromate in acid. all the ethanol fromcontain other
the beverage oxidisable
has left the sample substances that could interfere
2 Cr2O7 + 16 H + 3 C2H5OH → and reacted with with the titration,
the dichromate. the dichromate solution is placed in
Since this transfer
This method uses a3+redox
4 Cr + 11 H2Otitration
+ 3 CH3COOH to find the takes time, it is necessary to leave the flask with the
suspended sample a inflask
a warm and
placethe alcoholic beverage sample is suspended
overnight.
concentration
The amount ofofethanol in an aqueous
unreacted dichromate is then solution. The
in a small container above it (see diagram). The water
determined by adding potassium iodide solution which
ethanol isisalso
oxidised to ethanoic acid by reacting
oxidised by the potassium dichromate forming it with
Equipment Needed
and ethanol slowly evaporate and as the ethanol comes
an excess of potassium dichromate in acid.
iodine.
in contact
250 mL conical flasks with rubberwith
stoppersthe dichromate it first dissolves, and is
Cr2O72− + 14 H+ + 6 I− → 2 Cr3+ + 3 I2 + 7 H2O burette then oxidised. More ethanol evaporates until eventually
The 2 Cr2is O + 16 H+ + 3 C2Hsolution OHof→ 5 mL beakers or small
2−
iodine then
7 titrated with a standard glass vials
sodium thiosulfate
5 all the ethanol from the beverage has left the sample and
3+ and the titration results are used to
4 Cr + 11 H
calculate the ethanol content
O + 3 CH
2 of the original
COOH
3 solution.
beer or wine sample
reacted with the dichromate. Since this transfer takes
10 mL and 1 mL pipettes
2 S2O3 + I2 → S4O6 + 2 I
2− 2− − time, it is necessary to leave the flask with the suspended
incubator (optional)
Because alcoholic beverages such as wine or beer sample in a warm place overnight.
contain other oxidisable substances that could interfere
with the titration, the dichromate solution is placed in Solutions Needed

Rubber stopper
Equipment Needed
Acid dichromate solution: (0.01 molL-1 in 5.0 molL-1
sulfuric acid) (see safety notes). Add 125 mL of water
to a 500 mL conical flask. Carefully add 70 mL of
250 mL conical flasks with rubber stoppers
concentrated sulfuric acid with constant swirling. Cool
flask under cold water tap and add 0.75 g of potassium
burette
dichromate. Dilute to 250 mL with distilled water.
5 mL beakers
Starch indicator solution: or small
(1.0% solution) Dissolve glass
1.0 g vials
of soluble starch in 100 mL of recently boiled water. Stir
250 mL Conical flask until dissolved. beer or wine sample
(wide mouth)
Glass hook
Sodium thiosulfate
10solution:
mL and (0.03molL -1
). Add 7.44 g of
1 mL pipettes
Na2S2O3.5H2O to a 1L volumetric flask, dissolve in distilled
incubator
water and dilute up to the mark. (optional)
Potassium iodide solution: (1.2molL-1) Dissolve 5 g of KI
in 25 mL of water.
Sample holder

Acid dichromate
solution

1
 Method Needed
Solutions Figure 1 Experimental
Figure
oxidation
1 Experimental
of ethanol.
setupsetup
Conical
for
flask
Method Figure 1 Experimental
for oxidation
contains
oxidation yellow
of acid
ethanol.
setup for
of ethanol.
dichromate
Conical flask
Acid dichromate solution: (0.01 molL-1 in 5.0 molL-1 Conical flask containssetupyellow
Method
Sample Preparation Figure 1 Experimental
solution
contains and
yellowis
acid1dichromate
oxidation sealed
acid with
of ethanol. solution
for
rubber
dichromate
Conical and
flask
sulfuric
Sample
1.Methodacid)
Dilute (see samples
beer safety notes).
Preparation AddmL125inmL
1:20 (10 200ofmL)
water
with Figure
stopper.
solution Experimental
Small
and isbeaker
sealed setup for
containing
with rubber
contains
is yellow
sealed with acid dichromate
rubber stopper.
toSamplea 500
1.distilled mL
Dilutewater.conical
Preparation
beer samples flask. Carefully
1:20 (10 mL add in 70200mL mL)ofwith oxidation
beverage
solution
of ethanol.
sample
stopper. Small
and
Conical
is suspended
isbeaker
sealed
flask
containing above
with rubber
Small
contains beaker
yellow containing
acid dichromate
concentrated
1.Sample
distilled Dilute sulfuric
Preparation
water. beer samples acid 1:20
with(10 constant
mL in 200 swirling.
mL) with Cool from hook
beverage
stopper. in
sample
Small rubber
is
beaker stopper.
suspended
containing above
2. under Dilutecold winewater samples 1:50 add(20 mL ing1000 mL) with beverage
solution
from hookandinsample
isrubber is suspended
sealedstopper.
with rubber
flask
distilled water. tap and 0.75 of potassium beverage sample
aboveSmall
stopper. from is suspended
hook
beaker in rubberabove
containing
1.2.
distilled Dilute
Dilutewater. beer samples
wine samples 1:20 (10
1:50with(20mL mL inin200
1000 mL)
mL)with with
dichromate. Dilute to 250 mL distilled water. from hook
beverage
stopper.
in rubber stopper.
sample is suspended above
distilled
distilled
2. Dilutewater.
water. wine samples 1:50 (20 mL in 1000 mL) with from hook in rubber stopper.
Starch
Titration indicator(described solution: for (1.0%
one solution) Dissolve 1.0 g
beverage) Figure 2 Titration of the iodine
distilled
2. Dilutewater. wine samples 1:50 (20 mL in 1000 water.
mL) with Figure
formed. 2 The2 Titration
left flask ofiodine
showsthethe
ofTitration
soluble starch (described in 100for mLone of recently
beverage) boiled Stir Figure Titration of the
1. Transfer
distilled water.10 mL of the acid dichromate solution (see iodine
brown-coloured
formed. Theformed.
left The
solution
flask left
shows flask
resulting
the
until dissolved.
Titration (described for one Figure 2 Titration of the iodine
1.safetyTransfer
notes) to10amL 250ofmL acidbeverage)
theconical dichromate
flask with matching solution (see from
showsthe
brown-coloured
formed. formation
the of
solutioniodine.
brown-coloured The
resulting
Sodium thiosulfate solution: (0.03molL -1
). Add 7.44g(see Figure
right 2 The
flask
left flask
Titration
shows how
shows
of of
the iodine
the
the
brown
Titration
safety
1.rubber notes)
Transfer (described
stopper. to a 250 mLfor one
conical beverage)
flask
10 mL of the acid dichromate solution with matching solution
from the
brown-coloured
formed. The
resulting
formation
left solution
flask
from
iodine.
shows
the
The
resulting
ofsafetyNa S O .5H O to a 1L volumetric flask, dissolve in (see colour
right fades
flask
formation toofpale
shows howyellow
iodine.the asthe
brown
The the
right
1.rubber
2.
stopper.
2notes)
2 Transfer
3
Pipette 2to
1 10
mL
amL250ofmL
of the the conical
diluted
flask with matching
acid dichromate
beverage solution
sample into
from
iodine
colour
the
brown-coloured
is
formation
titrated
fades with
to pale
of
solutioniodine. The
resulting
thiosulfate
yellow as the
distilled
rubber watertoand
stopper. dilute up to the mark. flask
right
from shows
flask shows howhow the
the brown
brown
safety
2. sample
the notes)
Pipette 1 mL
holder.a 250ofThismLcan
the conical
diluted flask
be abeverage
5mL withsample
beaker matching
or into
glass (this
iodine isthe
the
is formation
stage
titrated at
withofthiosulfate
iodine.
which The
starch
colour
colour
right fades
flask fades
shows to
to pale pale
howyellow
theyellow
as the
brown
Potassium
rubber
the
2. sample iodide
stopper. holder. solution:
ofThis
the can (1.2molL
dilutedbe
vial. Prepare three samples of the beverage as theinto
Pipette 1 mL a 5mL
-1
beverage ) Dissolve
beaker sampleor 5 g of KI
glass
entire
solution
(this
as isthe
iodine is should
the stagebe
titrated
iodine at added).
is which
with starch
thiosulfate
titrated
colour
solution fades to pale
should be yellow
added). aswith
the
inthe
vial.25 sample
contentsmL ofofwater.
Prepare three
holder.
the samples
Thisarecan of
bethe beverage
inabeverage
5mL beaker asorthe entire
glass (this is the
thiosulfate stage at
(this which starch
withisthiosulfate
the stage at
2. Pipette 1 mLflask of the used
diluted the titration.
sample into iodine
Figure
solution
is titrated
3 Upon
should addition of starch the
contents
vial.
the Prepare of the
three flask are
samples used of in
the the titration.
beverage as the entire which
(this is the stagebe
starch at added).
solution should
which starch
3. sample Suspend holder. This can
the sample be a 5mL
holder overbeaker or glass
the dichromate solution
Figure takes
3 Upon on a
shouldaddition
blue-black
of starchcolour
the
Method
contents
vial.
3. Prepare
solution Suspend of thethe
andthree
flask
hold sample
in
are used
samples
placeholderwith
in the
of the theover titration.
beverage as the entire
the dichromate
rubber stopper (see due
be added).
solution
to
solution
Figure the
be added).
formation
takes addition
3 Upon of a
on a blue-blackstarch-
of starchcolour
the
contents of the flask are used in the titration. iodine
due to complex.
the formation of a starch-
solution
3.
figureSuspend
Sample and hold
1).Preparation in placeholder
the sample with the overrubber stopper (see
the dichromate solution
Figure
Figure takes
3 Upon
3 Upon on a blue-black
addition
addition colour
of the
of starch
iodine
due to complex.
the formation of atakes
starch-
figure
solution
3. Suspend 1). and hold
the in place
sample with
holder the rubber
over the (an stopper (see
dichromate starch
solution the
takes solution
on a blue-black on a
colour
1. 4.
figure
Store
Dilute beer
1). and
thesamples
flask overnight
1:20 (10 at 25–30°C
mL in 200 mL) incubator
with iodine
due to complex.
the formation
blue-black colourofdue a starch-
to the
solution
4.distilled
is Store
ideal). the hold
flask inovernight
place withatthe rubber(an
25–30°C stopper
incubator(see
water. iodine complex.
formation of a starch-iodine
figure
is ideal).
4. 1). the flask overnight at 25–30°C (an incubator
Store
2. 5.Dilute Next winemorningsamples allow 1:50the (20flask
mL in to 1000
comemL) to room
with complex.
is
4.
5. ideal).
Store
Next water.the
morning flask overnight
allow the at 25–30°C (an incubator
temperature,
distilled then loosen theflask
stopper to come carefully to roomand
is
5.
removeideal).
temperature,
Next and morningthen loosen
discard allow
the sample theflask
the stopper to come
holder. carefully to roomand
Titration
remove
temperature, (described
and discard
then loosen for one
the sample beverage)
theflask holder.
stopper carefully and
5.
6. Rinse Next morning
the wallsallow of thethe flask with to come
distilled to water,
room
1. remove
Transfer
temperature, and10 mL
discard of the
the acid
sample dichromate
holder. solution (see
6.
then Rinseadd about thethen 100loosen
walls of the
mL of theflaskstopper
distilled with
water carefully
distilled
and 1water,and
mL of
safety
remove notes) to a 250 mL conical flask with matching Figure 4 As more thiosulfate is
then Rinse
6.
potassium addand about
thediscard
iodide 100
walls the
mL
of the
solution. sample
of Swirlholder.
distilled
flask towater
with mix. and 1water,
distilled mL of
rubber stopper. added
Figure and
4 Aswe
morenear the titration
thiosulfate is
potassium
then
6. add about
Rinse iodide
the 100
walls solution.
mL
of the Swirlwith
of distilled
flask towater
mix. and 1water,
distilled mL of endpoint, the blue-black colour
7.
2.potassium Prepare
Pipette 1mL 3ofblank
the titrations
diluted by adding
beverage sample 10 mL of acid
into the
added and
Figure 4 Aswe
morenear
thiosulfate is from
the titration
then
7. add
Prepare iodide
about 3 100
blank solution.
mL of
titrations Swirl
distilledby to mix.
water
adding and
10 mL1 mL of
of acid the starch-iodine
endpoint, the complex
blue-black fades.
colour from
dichromate
sample holder. solution This to a conical
can beSwirl a 5 mL flask,
beaker or glassmL
adding 100 added and
4 As4we
Figure
Figure Asnear
more morethethiosulfate
titration
thiosulfate is
potassium iodide solution. to mix. the starch-iodine
endpoint, complex fades.
dichromate
7.
of Prepare
water and solution
3
1 blank
mL of to a conical
titrations
potassium
vial. Prepare three samples of the beverage by flask,
adding
iodide adding
10 mL
solution 100
asof
and mL
acid
the andthe
is added
added blue-black
and
we wethe
near near colour
the from
titration
the starch-iodine complex
titrationtheendpoint,
blue-blackthe fades.
blue-
of water
dichromate
swirling
7. and
to mix.
Prepare 1 mL
solution
3 blank of potassium
to aflask
conical
titrations iodide
byflask,
adding solution
adding
10 mL and
100 mL
of acid endpoint, colour from
entire contents of the are used in the titration. theblack colour from
starch-iodine the fades.
complex starch-
swirling
of water to
dichromate and mix. 1 mL of potassium
solution to a conical iodide
flask, solution
adding andmL
100
3. 8. Fill a burette
Suspend
swirling the sample withholder
sodiumover thiosulfate
the dichromate solution iodine complex fades.
of
8.solution
and Fill to
water
titrateaand mix.
each 1 mLflask
burette of
withpotassium
sodium
with sodium
and hold in place with the rubber
iodide
thiosulfate solution
thiosulfate. solutionand
When
stopper
swirling
and titrateto mix.
each
8.
the Fill
brown
(see figure 1). flask
a burette
iodine withwith
colour sodiumsodium
fades thiosulfate.
tothiosulfate
yellow When
solution
(figure 2), add
the
1 mLbrown
and
8. titrate
of
Fillstarch iodine
each
a burette colour
flask
solutionwithwith fades
and
sodiumsodium
keep tothiosulfate
yellow (figure
thiosulfate.
titrating until 2), add
When
the
solution blue
4. Store
1and
the mL of
brownthe
starch flask
iodine overnight
solution
colour and at
fades 25–30°C
keep to titrating
yellow until
(figure the
2), blue
add
colour disappears
titrate each flask (figures
with 3-5).
sodium Titrate the blankWhen
thiosulfate. flasks
1the(an
colour incubator
mLbrown
of disappears
starch is ideal).
solution(figures and 3-5).
keep Titrate
titrating the(figure
blank
until flasks
the blue
first, and repeat
iodine until
colour concordant
fades to results
yellow are obtained
2), add Figure 5 The endpoint of the
5. colour
Next
first,
1(titres morning
and
mL ofagreeingrepeat
disappears
starch solution allow
until
to within the
and flask
concordant
(figures 3-5).
0.1keep to come
results
Titrate
mL).titrating the
Then titrate to
are room
obtained
blank
untileach flasks
of the
the blue titration is reached
Figure 5 The when
endpoint just
of the
temperature,
(titres
first,
alcohol
colour and repeatthen
agreeing
samples.
disappears tountil loosen
within 0.1
concordant
If(figures
the three the
3-5).mL). stopper
samples Then
results
Titrate of
the carefully
titrate
are
the each
obtained
beverage
blank and
of the
flasks do enough
titration thiosulfate
is reached is added
when
Figure 5 The endpoint of the justto react
remove and discard the sample holder. with
enoughall the iodine
thiosulfate present
is addedandto the
react
alcohol
(titres
not give
first, samples.
agreeing
andconcordant to If the
within
repeat untilresults, three
0.1
concordant samples
mL).
further Then of
samples
results the
titrate beverage
will needdo
each
are obtained of the
to titration
Figure
Figure is reached
5the5 iodine
The The when
endpoint
endpoint just
of theof the
solution
with
enoughall becomes
thiosulfate colourless.
present
is addedand the
6. Rinse the walls of the flask with distilled water, thento
not give
alcohol
be prepared.
(titres concordant
samples.
agreeing to If theresults,
within three
0.1 further
samples
mL). Then samples
of the
titrate will
beverage
each need
of do
the titration is
titration
solution reached when
is reached
becomes justto just
when
colourless.
react
with all the iodine present and the
be
not prepared.
give
alcohol
add concordant
samples.
about 100 mL If theresults,
of three further
distilled samples
water samples
of
and will needdo
the beverage to enough
enough
solution
thiosulfate
becomes
is added
thiosulfate to react
is added
colourless.
with
to react with all the iodinethe
all the iodine present and
be
not prepared.
give
1 mL of concordant
potassium iodide results,solution.
further samples Swirl to will mix.need to solution becomes colourless.
present and the solution
7. bePrepare
prepared. 3 blank titrations by adding 10 mL of acid becomes colourless.
dichromate solution to a conical flask, adding 100
mL of water and 1 mL of potassium iodide solution
and swirling to mix.
8 Fill a burette with sodium thiosulfate solution and
titrate each flask with sodium thiosulfate. When the

2
2
2
brown iodine colour fades to yellow (figure 2), add 1mL Contact Us
of starch solution and keep titrating until the blue
colour disappears If you have any questions or comments relating to this
(figures 3–5). Titrate the blank flasks first, and repeat experiment, please contact us. Please note that this
until concordant results are obtained (titres agreeing service is for senior school chemistry students in New
to within 0.1 mL). Then titrate each of the alcohol Zealand only. We regret we are unable to respond to
samples. If the three samples of the beverage do not queries from overseas.
give concordant results, further samples will need to be Outreach
prepared. College of Science
University of Canterbury
Private Bag 4800
Result Calculations Christchurch
The blank titration tells you how much acid dichromate New Zealand
was present at the start. As no alcohol was added the Phone: +64 3 364 2178
full amount of the dichromate is still present. The Fax: +64 3 364 2490
blank titrations are carried out so the result can be Email: outreach@canterbury.ac.nz
compared with those of the sample titrations. www.outreach.canterbury.ac.nz
1. Determine the average volume of sodium
thiosulfate used for your sample from your
concordant sample results.
2. Determine the average volume of sodium
thiosulfate used for the blank titration from your
concordant blank results.
3. Subtract the volume of the sodium thiosulfate
solution used for the sample titration from the
volume used for the blank titration. This volume
of the sodium thiosulfate solution is now used to
determine the alcohol concentration.
4. Calculate the number of moles of sodium
thiosulfate in this volume.
5. Using the equations, determine the relationship
between the moles of sodium thiosulfate and the
moles of ethanol.
– as 6 mol of S2O32- is equivalent to 1 mol of Cr2O72-
– and 2 mol of Cr2O72- is equivalent to 3 mol of
C2H5OH
– then 1 mol of S2O32- is equivalent to 0.25 mol of
C2H5OH
6. Use this ratio to calculate the moles of alcohol in the
sample solution.
7. Remember to allow for the dilution factor
eg. if the dilution was 1:20 the result needs to be
multiplied by 20.
8. Convert the answer in moles per litre to percentage
(grams per 100mL) to compare with the figure given
on the bottle of the alcoholic beverage tested.