College of Science

Determination of Chloride Ion Concentration by Titration

(Volhard’s Method)
Safety neutral or basic, Mohr’s method or the gravimetric
method should be used. The method is illustrated
Lab coats, safety glasses and enclosed footwear must below by using the procedure to determine the
be worn at all times in the laboratory. concentration of chloride (from sodium chloride)
Silver nitrate solution causes staining of skin and in cheese.
fabric (chemical burns). Any spills should be rinsed
with water immediately. Equipment Needed
Concentrated nitric acid is very corrosive: take great
boiling chips
care using the 6molL-1 solution.
500 mL volumetric flask
10 mL and 100 mL measuring cylinders
Introduction
conical flasks
Determination of Chloride Ion Concentration
This method uses a back titration with potassium
thiocyanate to determine the concentration of chloride Bunsen burner, tripod and gauze
by Titration (Volhard’s Method)
ions in a solution. Before the titration an excess volume burette and stand
of a silver nitrate solution is added to the solution 50 mL pipette (if possible)
containing chloride ions, forming a precipitate of silver
chloride. The term ‘excess‘ is used as the moles of silver
Introduction
nitrate added are known Thisto exceed
method usesthe moles
a back ofwith
titration sodium
potassium
chloride present in the thiocyanate
sample so to determine
that all the
theconcentration
chloride of chloride
ions in a solution. Before the titration an excess volume Burette containing
ions present will react. of a silver nitrate solution is added to the solution potassium thiocyanate
containing chloride ions, forming a precipitate of silver solution
Ag+(aq) +chloride.
Cl–(aq)The→term
AgCl
‘excess‘
(s) is used as the moles of silver
nitrate added are known to exceed the moles of sodium
The indicator Fe3+ (ferricchloride
ion) ispresent
theninadded and
the sample theall the chloride
so that
solution is titrated with the potassium thiocyanate
ions present will react.
solution. The titrate remains pale yellow → excess
as–(aq)the
Ag+(aq) + Cl AgCl(s)
(unreacted) silver ions react withFethe(ferric
The indicator 3+
thiocyanate ionsand the
ion) is then added
solutionprecipitate.
to form a silver thiocyanate is titrated with the potassium thiocyanate
solution. The titrate remains pale yellow as the excess
(unreacted) silver ions react with the thiocyanate ions to
Ag +
(aq)
+ SCN –
form a(aq) →
silver AgSCNprecipitate.
thiocyanate (s)
Once all the silver ions have reacted,Ag+(aq) the
+ SCN slightest
–
(aq)
→ AgSCN(s)
excess of thiocyanate reacts
Once allwith Feionstohave
the silver
3+
form a dark
reacted, red
the slightest
complex. excess of thiocyanate reacts with Fe3+
to form a dark red
complex.
Fe3+(aq) + SCN–(aq) →Fe[FeSCN]
(aq)
+ SCN 2+
3+
(aq)
→ [FeSCN]
– 2+
(aq)
(aq)
The concentration of chloride ions is determined by
The concentration of chloride
subtractingions is determined
the titration bymoles of silver
findings of the
subtracting the titration findings of the moles of silver
ions that reacted with the thiocyanate from the total Conical flask
moles of silver nitrate added to the solution.
ions that reacted with the thiocyanate from the total
This method is used when the pH of the solution after
moles of silver nitrate added tohas
the sample thebeensolution.
prepared is acidic. If the pH is
Cheese extract solution
neutral or basic, Mohr’s method or the gravimetric
This method is used when the pH of the solution, after
method should be used. The method is illustrated below
the sample has been prepared,
by using theisprocedure
acidic.toIfdetermine
the pH the
is concentration
of chloride (from sodium chloride) in cheese.

Equipment Needed
boiling chips
Solutions Needed and addition of 5 mL of potassium permanganate
should be continued, checking each time until there
Solutions
ConcentratedNeeded
nitric acid (see safety notes): (6 mol L-1) 4. Cool the solution and filter it. Wash the solid
is a satisfactory level of digestion.
residue with a few mL of distilled water.
Silver nitrate solution:
Concentrated nitric acid(0.1 mol
(see L−1). Ifnotes):
safety possible, dry L5-1g) of
(6 mol 4. Cool the solution and filter it. Wash the solid residue
AgNO3 for 2 hours at 100°C and allow to cool. Accurately 5. withMake themL
a few filtrate up to 500
of distilled mL in a volumetric
water.
Silver nitrate solution: (0.1 mol L
weigh about 4.25 g of solid AgNO3 and dissolvedry
−1
). If possible, 5 g of
it in flask.
AgNO
250 mL for 2 hours at 100°C and allow to cool. Accurately
3 of distilled water in a conical flask. Store the
5. Make the filtrate up to 500 mL in a volumetric flask.
weigh
solution in a 4.25
about brown solid AgNO3 and dissolve it in 250
g ofbottle. Titration
Titration
mL of distilled water in a conical flask. Store−1the solution
Potassium thiocyanate solution: (0.1 mol L ). Weigh 1. UseUse
1. a volumetric
a volumetric cylinder
cylinder toto measure
measure 100100mLmL ofof the
the
in a brown bottle.
2.43 g of solid KSCN and dissolve it in 250 mL of cheese extract solution (be as precise as
cheese extract solution (be as precise as possible) possible) and
Potassium thiocyanate
distilled water solution:
in a volumetric flask.(0.1 mol L−1). Weigh pourandit pour
into aitconical flask. flask.
into a conical
2.43 g of solid KSCN and dissolve it in 250 mL of distilled
Potassium permanganate solution: (5%) Add 1.5 g 2. Add
2. Add 1 mL
1 mL of of saturated
saturated ferric
ferric ammonium
ammonium sulfate
sulfate
water in a volumetric flask.
KMnO4 to 30 mL of distilled water. solution as indicator.
solution as indicator.
Potassium permanganate
Ferric ammonium solution: (saturated)
sulfate solution: (5%) Add 1.5Add
g 8g
3. Titrate
3. Titrate
thethe unreacted
unreacted silver
silver ionsions
withwith
thethe0.10.1
molmolL−1
KMnO to 30 mL of distilled water.
of NH 4Fe(SO ) .12H2O to 20 mL of distilled water and
4 42 L−1 potassium thiocyanate solution. The end point point isisthe
the
add a ammonium
Ferric few drops of sulfate
concentrated nitric
solution: acid (seeAdd
(saturated) safety
8g first
first appearance
appearance of aofdark
a darkredred colour
colour duedue to the
to the ferric
ferric
notes).
of NH4Fe(SO4)2.12H2O to 20 mL of distilled water and add thiocyanate
thiocyanate complex
complex (figure
(figure 1). 1).
a few drops of concentrated nitric acid. 4. Repeat thethe
titration with 100100mLmL samples ofofthethe
4. Repeat titration with samples
Method cheese
cheese extract
extract solution
solution untiluntil
youyou obtain
obtain concordant
concordant
Method
Sample Preparation
results (titres agreeing within
results (titres agreeing within 0.1 mL). 0.1 mL).

The salt sodium

Sample chloride is added during the
Preparation
manufacture
The salt sodium of cheddar
chloride ischeese.
addedInduringthis method,
the
manufacture of cheddar cheese. In thissalt
the cheese is ‘digested’ to release this to obtain
method,
the cheese
the concentration of chloride
is ‘digested’ to releaseions.this
To salt
carrytoout this
obtain
digestion, the cheese is reacted with
the concentration of chloride ions. To carry out this nitric acid and
potassiumthe
digestion, permanganate.
cheese is reacted The chloride
with nitric ions areand
acid then
‘free’ to form a precipitate with the
potassium permanganate. The chloride ions are then added silver ions.
1. Cuttoorform
‘free’ gratea the cheese into
precipitate withfine pieces silver
the added and ions.
accurately weigh about 6 g into a 500 mL conical
1. Cut or grate the cheese into fine pieces and
flask.
accurately weigh about 6 g into a 500 mL conical flask.
2. Precisely add 50 mL of 0.1 mol L−1 silver nitrate
2. solution
Precisely (by pipette if possible), 20 mL ofnitrate
add 50 mL of 0.1 mol L silver
−1

solution (by pipette

concentrated if possible),
nitric acid, (very20carefully
mL of concentrated
– see
nitric (very carefully – see safety
safety notes), 100 mL of distilled water and100
acid, notes), a fewmL Figure 1 Left flask: before the titration endpoint, addition of SCN−
of distilled Figure 1 Left flask: before the titration endpoint, addition of
boiling chips, and heat the solution to boiling inthe
water and a few boiling chips, and heat a ions −leads to formation of silver thiocyanate precipitate, making the
SCN ions leadsHere
to formation ofalso
silver thiocyanate precipitate,
solution
fumehood.to boiling. solution cloudy. the solution takes a faint yellow colour due
making the solution
to the colour of the cheesecloudy. Here
extract. the solution
Centre flask: at the also takes aall the
endpoint
3.
3. AsAsthethe solution
solution boils
boils addadd5 mL5 mLofof5%5% potassium
potassium faint yellow
free silver ionscolour due precipitated
have been to the colour by of
SCN the
− cheese extract.
. The slightest excess of
permanganate solution. This addition
permanganate solution. This addition will will cause a very
cause a Centre
SCN forms
− flask: at the
a dark redendpoint all the free
coloured complex withsilver
the Feions
3+
ionshave
frombeenthe
smelly precipitated
ferric ammonium by SCN −
. The
sulfate slightest
indicator, excess
giving of SCN− aforms
the solution slightaorange/
very reaction and should
smelly reaction be done
so done in thein fumehood.
a fumehood.Keep
Keep boiling until dark red coloured
red colouration. complex
Right with theofFeSCN
flask: If addition ions
3+ −
from thepast
is continued ferricthe
boiling until thethe purple
purple colour
colour disappears,
disappears, then
then add ammonium
endpoint, further sulfate
ferricindicator,
thiocyanate giving the is
complex solution
formed and a slight
a stronger
addanother
another5 5mL mLofofpotassium
potassiumpermanganate
permanganatesolution. solution. dark red colour
orange/red results. NB:Right
colouration. The titration
flask: Ifshould
addition be stopped
of SCNwhen−
is the
Continue
Continue thisthis
process
process until 30 30
until mLmL of potassium
of potassium first trace ofpast
continued dark the
red colour is observed.
endpoint, furtherUsing
ferrican incompletelycomplex
thiocyanate titrated
permanganate
permanganate solution
solutionhashasbeen added
been added andand thethe reference flask for comparison is a helpful way
is formed and a stronger dark red colour results. NB: The to identify the first
cheese appearance of red be
colouration.
cheese particles are completely digested (or close
particles are completely digested (or as as close titration should stopped when the first trace of dark red
as as
possible).
possible). To To
find outout
find whenwhen digestion
digestion is complete,
is complete, colour is observed. Using an incompletely titrated reference
remove
remove thethe flask from
flask fromheat andand
heat allow
allow it toit stand
to stand for for
a a flask for comparison is a helpful way to identify the first
fewfewmoments.
moments. Undigested
Undigested cheese
cheese particles
particles willwill
float
float appearance of red colouration.
uponuponthethesurface
surfaceof the clear
of the liquid,
clear while
liquid, thethe
while whitewhite
precipitate
precipitate of silver chloride
of silver chloridewillwill
sinksinkto the
to thebottom.
bottom. If If
there is still
there tootoo
is still muchmuch undigested
undigested cheese,
cheese, thetheboiling
boiling
and addition of 5 mL of potassium permanganate
should be continued, checking each time until there is a
satisfactory level of digestion.
Result Calculations Contact Us
1. Determine the average volume of potassium If you have any questions or comments relating to this
thiocyanate used from your concordant titres. experiment, please contact us. Please note that this
2. Calculate the moles of potassium thiocyanate used. service is for senior school chemistry students in
New Zealand only. We regret we are unable to respond
3. Use the equation of the reaction between silver ions to queries from overseas.
and thiocyanate ions
Outreach
Ag +
(aq)
+ SCN
–(
aq)
→ AgSCN(s) College of Science
to calculate the moles of unreacted silver nitrate in University of Canterbury
100 mL of cheese extract, and multiply the figure by Private Bag 4800
five to determine the total moles of unreacted silver Christchurch
nitrate (the excess) in the 500 mL volumetric flask. New Zealand
Phone: +64 3 364 2178
4. Calculate the moles of silver nitrate in the 50 mL Fax: +64 3 364 2490
of solution that was added during the sample Email: outreach@canterbury.ac.nz
preparation to the cheese. www.outreach.canterbury.ac.nz
5. Calculate the total moles of silver nitrate that reacted
with the salt from the cheese by subtracting the
moles of unreacted silver nitrate (the excess) from
the total moles of silver nitrate added to the cheese.
6. Use the equation of the reaction between the silver
ions and the chloride ions to calculate the moles of
sodium chloride in the sample of cheese.
Ag+(aq) + Cl–(aq) → AgCl(s)
7. Calculate the concentration of sodium chloride in the
cheese as grams of salt per 100 g cheese (% salt).

Additional Notes
1. Residues containing silver ions and precipitate are
usually saved for later recovery of silver metal. Check
this with your teacher or the laboratory supervisor.
2. A ‘blank’ titration substituting sucrose (sugar) for the
cheese should be carried out to see if there are any
‘contaminating’ chloride ions present in the reagent
solutions used. If any are found, the figure should be
subtracted from the titration results.
3. For greatest accuracy it is a good idea to standardise
your thiocyanate solution by titrating several
samples against your standardised silver nitrate
solution (once again using ferric ammonium sulfate
indicator). The concentration of SCN– determined by
this titration should then be used in all calculations.