Improving Titrations

Read Chapters 11 and 12

Chemistry 21

Acid/Base titration for NaOH

You have an old bottle of HCl that says
it is about 37% (by weight? volume?)
We have to know the exact
concentration of the HCl in order to
titrate the NaOH.

Chemistry 21

Standardization of Reagents
All our measurements are made with
reference to standards
The accuracy of a result is only as good as
the quality and accuracy of the standards
used
A standard is a reference material whose
purity and composition are well known and
well defined
Chemistry 21

Primary Standards
Used as titrants or used to standardize
titrants
Requirements:

Usually solid to make it easier to weigh

Easy to obtain, purify and store, and easy to dry
Inert in the atmosphere
High formula weight so that it can be weighed with
high precision

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Primary standard solutions

Accurately weigh primary standard and
dissolve in known volume to get known
concentration
Use directly as titrant
Use to standardize titrant
Titrate primary standard solution and use the
volume required to calculate concentration
of titrant eg. CaCO3 solution used in analysis
of Ca with EDTA
Chemistry 21

Secondary standard solutions

A solution standardized against a primary

standard solution
Make titrant up to an approximately known
concentration
Standardize with primary standard
eg the EDTA titrant,
HCl is not a primary standard since HCl slowly
evaporates
NaOH is not a primary standard because it absorbs
CO2 to make CO3 2- which changes its base strength.

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Standard Solutions
Standard Reference Materials (SRM)
can be purchased from various
government agencies
$$$$!!
Balances require the purchase of a
calibration kit of weights.

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Back to our problem

We dont have time or money to order a
standard reference solution
However, there is an old bottle of
Na2CO3 in the lab maybe we could
use that?
Titration reaction would be
Na2CO3 + 2HCl 2Na2+ + 2Cl-+ CO2 +
H2O
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Chemistry 21

Chemistry 21

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Preparation of a primary standard

Dry some Na2CO3 in an oven (at least 100C, less

than 851C) until a constant weight is reached upon
cooling.
This gets rid of water and converts any NaHCO3 to Na2CO3.

Accurately weigh required amount on a calibrated

scale.
Using a solids funnel, transfer solid to a clean,
calibrated volumetric flask.
Add a small volume of water to dissolve, then dilute
to mark.
Invert at least 10X then keep tightly capped.
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How much Na2CO3 do I need?

We usually try to use acid at about 0.01M.
We try to make titrations use about 25 mL of
titrant and 25 mL of sample.
10mmol 1Na2CO3
1
25mLx
x
x
0.005M Na2CO3
mL
2HCl
25mL
0.005mol
g
x0.250 Lx105.99
0.132 g Na2CO3
L
mol
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How much HCl do I need?

Bottle is 37% HCl
probably by weight.
This means in 100g
of solution, I have
37g of HCl and 63g
of H2O.

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mol
37 gx
1.01mol
36.46 g
mL
63 gx
0.063L
1g
1.01mol
~ 16 M
0.063L

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How much HCl do I need?

16M is too concentrated we want about 0.01M.

1L 0.01M xL 16M
x 0.62mL

0.62 mL is too small for us to measure accurately unless

we have micropipettes, so we will do a dilution:
Using a graduated cylinder, measure ~6.25 mL of 16M acid.
Dilute to 100 mL = ~ 1 M HCl.
Using a graduated cylinder, measure 10 mL of 1M acid and dilute
to 1000 mL = ~0.01 M HCl.

Why dont we have to use a volumetric flask and pipettes?

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Why store acids in plastic bottles?

Ions adsorb (stick to) the surface of

glass.
H+ will compete for these ion exchange
sites
Can lead to impurities in your solution
and lower concentration of H+ than you
wanted!
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How to determine endpoint

Easiest way is to use an indicator (a
weak acid or base) which has a colour
change in the pH region where you
expect your equivalence point to be.
We expect an equivalence point
between ph 4 and 5 (from literature).
Which one should we choose?
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Bromocresol Green

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http://www.usca.edu/chemistry/spectra/brmcrgrn.htm

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Colour change for Bromocresol Green

Finish ?
Start

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http://inst.santafe.cc.fl.us/~chem/intbl.html

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End point determination

Most likely, we are going to look for the
first hint of green that we can see

Something like
this?

Chemistry 21

www.survivalarts.com/archives/2004_02.html

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End point determination

This is going to be difficult to see!
What about adding an intermediate
indicator to tell us when we are about
half way there when the carbonate
has been converted to bicarbonate?

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End point determination

The carbonate titrations will progress through an
intermediate end point using phenolphthalein
indicator which changes color at about the pH where
all carbonate has been converted to bicarbonate.
For a sample initially containing only carbonate, the
volume required to achieve the phenolphthalein color
change is close to half that required for the
subsequent bromocresol green end point.
It is not exactly half because the color change and
the equivalence point are not exactly the same.
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End point determination

So the solution will change from pink to
almost colourless (how do I know this?)
Does it matter if I overshoot this
endpoint?

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Performing the titration

Weigh out approximately 0.132 g of
Na2CO3. Record the exact weight.
Using a funnel, add the Na2CO3 to a
250 mL volumetric flask (check to see
that it is clean before starting!).
Add water to the way point and swirl
to dissolve. Then add water to the
mark. Invert at least 10 times to mix.
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Performing the titration

Prepare the 0.01 M HCl solution as
previously discussed.
Pipette 25 mL of Na2CO3 solution into a
clean Erlenmeyer flask.
Fill a clean, 100 mL burette with the
0.01 M HCl dont worry about getting
it to exactly 0.00 (takes too long and
more likely to induce error)
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Prepare a blank solution

This will help us know what the solution
will look like when all the carbonate has
been titrated.
Pipette 25 mL of distilled water into an
Erlenmeyer flask. Add three drops of
bromocresol green indicator.

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Prepare a blank solution

Place the flask on a
hot plate and boil for
approximately 1
minute to remove all
CO2.

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Prepare a blank solution

After cooling for a
few seconds and
swirling the flask,
place in an ice bath
to cool.

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Prepare a blank solution

Note the starting
reading on your
burette.
Slowly add a few
drops of acid, while
swirling, and note
the colour changes.

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Prepare a blank solution

Look for a point where it is
definitely not blue, but not
yellow either.
Wash down the sides of
the flask with distilled
water after each drop.
Note the final volume
this is the volume to
subtract from each titration.

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Prepare a blank solution

Cover the blank solution with parafilm
this will prevent atmospheric CO2 from
changing the colour back to blue.
Place solution on a piece of white paper
for best contrast.
Keep this solution as a comparison
point for future titrations.
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Performing the Titration

Add a few drops of
phenolphthalein to
the 25 mL of Na2CO3
solution.
Note the colour
change of the
solution.
Noting the initial
volume on burette,
start adding acid.
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Performing the Titration

Swirl solution after each
addition and wash down
sides frequently with
distilled water.
Continue to add acid
until you see a very light
pink.
Try not to overshoot,
but it really doesnt
matter too much.
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Performing the Titration

Now add a few drops of
bromocresol green and
compare to the blank.
Continue with titration,
remembering that you
are approximately half
done.

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Performing the Titration

Keep comparing to
the blank.
Try not to go beyond
the colour of the
blank or you may
irreversibly
overshoot.

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Performing the Titration

When you think you
are almost there
(colour change is
imminent!), boil the
solution to remove
any CO2.
This will raise the pH
so that you change
the colour back to
blue.
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Performing the Titration

Continue to add acid
until you match the
blank probably just
a few more drops.
Make sure you have
at least 3 titrations
with the nearly the
same volume.
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Now to titrate our sample!

We dont know the composition of the sample
so we assume it to be 50% NaOH, 50%
CaCl2.
Thus, we want to make a 0.01M solution:

0.01 mol/L x 0.250 L x 40.0 g/mol x 2 0.2 g

So, weigh out approximately 0.2 g (record
exact weight) of your sample and prepare it in
a 250 mL volumetric flask.
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Titration
This is a strong acid with a strong base
thus we expect the endpoint to be at
pH 7 exactly.
Phenolphthalein changes at pH 8 to 9
so it wont work.

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www.chemistry.wustl.edu/.../AcidBase/phph.htm

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http://cwx.prenhall.com/petrucci/medialib/media_portfolio/text_images/FG18_081C.JPG

Titrating the sample

So we are looking for an orange colour.
Fill the burette with HCl
Clean pipette and pipette 25 mL of unknown
solution into a clean Erlenmeyer flask.
Add a few drops of phenol red indicator (what
colour should your solution be?)
Slowly add acid until colour changes to
orange.
Why cant we use a blank in this case?
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Beckys titration tips

1. Deliberately overshoot the titration the first
time. This gives you an idea of where the
end point will be and saves you time and
frustration in the long run.
2. Continuously wash your sample with
distilled water to get any random drops from
the burette tip and glass sides.
3. Learn to use hanging drops and half drops
to get the colour change more precisely.
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Titration improvements
Create a pH 7 orange sample for
comparison
But we dont have any pH 7 buffer

What about a method that could

improve our accuracy a pH titration!

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The pH combination electrode

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www.greenair.com

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How a pH electrode works

Active part of the electrode is the extremely thin glass.
Surface of the glass is protonated by both internal and
external solution until equilibrium is achieved.
Both sides of the glass are charged by the adsorbed
protons, which leads to a potential difference.
This potential is directly proportional to the pH difference
between solutions on both sides of the glass.
The majority of commercial pH electrodes are combination
electrodes that have both glass and reference electrodes in one
housing.
Separate pH electrodes and reference electrodes are still used
they allow higher precision. In most cases combination
electrodes are precise enough and more convenient to use.

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How to do a pH titration
We need

A combination electrode
A pH meter
Standard buffer solutions for reference
A burette
A stirring mechanism

Advantages
No indicator needed
Exact endpoint determined by concentration

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pH titrations
Titrations of strong acids with strong
bases have an endpoint at pH = 7.00
Titrations using weak acids and bases
have endpoints above or below pH 7.
We need to discuss equilibrium for this

We are ignoring activity for now.

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So what do we know?
From previous experiment, we know that the
powder is somewhere around 78.3% 0.9%
NaOH.
Plan experiments for 78.3% NaOH

We already have some HCl that we know the

concentration is 0.01024 0.0004 mol/L
However, if it has been sitting for some time, we
may wish to repeat the standardization to confirm
the concentration.
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Experimental design
Prepare a 0.01M solution of NaOH
using the unknown powder.
Take a 25 mL aliquot of unknown NaOH
solution and titrate with 0.01 M HCl
What should my endpoint volume be?

Record pH and volume of titrant to plot

graph to determine the endpoint.
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Equivalence point somewhere in here

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