LU 5: Acid base titration

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Learning Objectives
At the end of this learning unit, students should be able to:

 Illustrate titration of a strong acid with a strong base

 Describe the difference between an “endpoint” and an
“equivalence point” in an acid-base titration
 Identify the equivalence point in an acid-base titration
from the pH titration curve
 Illustrate titration of a weak acid with a strong base.
Learning Objectives
Distinguish titration curve of polyprotic acids
with a strong base and polybasic base with a
strong acid.
Identify the equivalence point in an acid-base
titration from the pH titration curve.
Identify suitable indicator for an acid-base
titration.
Apply titration in Kjeldahl analysis
Evaluate Acid-Base Titrimetry
Defining Terms

 Standard solution: A reagent of a known

concentration which used in the titrimetric analysis

 Titration: This is performed by adding a standard

solution from burette or other liquid-dispensing device
to a solution of the analyte until the point at which the
reaction is believe to be completed
 Defining Terms
 Equivalence point: Occurs in a titration at the point in which
the amount of added titrant is chemically equivalent to the
amount of analyte in a sample

 Back-titration: This is a process in which an excess of the

standard titrant is added, and the amount of the excess is
determined by back titration with a second standard titrant.

In this instance, the equivalent point corresponds with the

amount of initial titrant is chemically equivalent to the amount of
analyte plus the amount of back titrant.

http://www.youtube.com/watch?v=YsavyASe7ho
 Defining Terms
 End point: The point in titration when a physical change
occurs that is associated with the condition of chemical
equivalence

 Indicators are used to give an observable physical change

(end point) or at near the equivalence point by adding them
to the analyte. The difference between end point and
equivalence point should be very small and this difference
is referred to as titration error.
 Defining Terms

 Titration error, Et

Et=Vep – Veq

Vep is the actual volume used to get to the end point.

Veq is the theoretical value of reagent required to reach
the end point.
 Acid-Base Titrations
Acid-Base Titrations

• A quick and accurate method for determining acidic

or basic substances in many samples.

• The titrant is typically a strong acid or base.

• The sample species can be either a strong or weak

acid or base.

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 Acid-Base Titration

1)strong acid – strong base titration

2)weak acid – strong base titration
3)strong acid – weak base titration
4) polyprotic acid – strong base titration
5) polybasic base – strong acid titration

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 Strong Acid - Strong Base Titration

In strong acid – strong base titration, there are three

regions of the titration curve that represent different
kinds of calculations :
- before equivalence point

- at equivalence point

- after equivalence point

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Titration curve

 Strong acid titrated with a strong base:

 The net reaction is

H3O++ OH- → 2H2O

• Before the equivalence point, acid is present in excess
• pH is determined by the concentration of excess HCl

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Strong acid titrated with a strong base
 At equivalence point, moles of acid and moles of base
are equal.
 At equivalence point,

[H3O+] = [OH- ]
pKw = 14 = pH + pOH
pH = 7

 So, the equivalence point for strong acid/base is always

a pH=7

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Strong acid titrated with a strong base

Overtitration
 Pass the equivalence point, we don’t have any acid
remaining. All that we are doing is diluting our titrant.

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Titration curve
 Eg. Construct a titration curve for the titration of 100 mL 0.1 M HCl with 0.1
M NaOH.
1) Volume of NaOH needed to reach eq. point
Moles HCl = moles NaOH
VNaOH = 100.0 mL
2) Before addition of NaOH
pH = - log [0.1] = 1
3) After addition of 10mL NaOH

After 10 mL NaOH

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Titration curve
4) At equivalence point
 Equivalence point, moles of HCl= moles of NaOH
 Since neither is in excess, pH is determined by Kw
Kw = 1.00 x 10-14 = [H3O+][OH-] = [H3O+]2
[H3O+] = 1.00 x 10-7
pH= 7

 Note that for the first 90 mL of titration, pH = 2.28

 At eq. point, the pH value jump of 4.72 pH unit

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Titration curve
5) Overtitration
 Accountfor the dilution of titrant
 10 mL overtitration

[OH-] = moles excess NaOH = MVNaOH- MVHCl

Vtotal
= (0.1M)(110mL)-(0.1M)(100mL)
210 mL
= 0.0048M

pOH = 2.32
pH = 14-2.32 = 11.68

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Titration of a Strong Acid with a Strong
Base
From the start of the
titration to near the
equivalence point, the
pH goes up slowly.

© 2009, Prentice-Hall, Inc.

Titration of a Strong Acid with a Strong
Base
Just before (and after)
the equivalence point,
the pH increases
rapidly.

© 2009, Prentice-Hall, Inc.

Titration of a Strong Acid with a Strong
Base
At the equivalence
point, moles acid =
moles base, and the
solution contains only
water and the salt
from the cation of the
base and the anion of
the acid.

© 2009, Prentice-Hall, Inc.

Titration of a Strong Acid with a Strong
Base
As more base is
added, the increase in
pH again levels off.

© 2009, Prentice-Hall, Inc.

Titration curve

Titration of a strong base with a strong acid:

 Ifwe plot pOH rather than pH, the result still look
identical.
 Typically, we still plot pH verses mL titrant, so the
curve is inverted.

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Titration curve
 [titrant] affects the shape of titration curve

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Titration curve
 [titrant] is reduced.

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Titration of weak acids & weak bases with
strong titrant
 Must concerned with conjugate acid/base pairs & their
equilibrium

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Titration of weak acids & weak bases with
strong titrant

Before titration:
 If the sample is weak acid, then use

 [H O+]=[A-]
3
 Calculate the pH value

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 Titration of weak acids & weak bases
with strong titrant

Before titration:
 If the sample is weak base, then use

 [OH-]=[HA]
 Calculate the pH value = 14 - pOH

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Titration of weak acids & weak bases
with strong titrant
Before equivalence point:
 Equilibrium expression used is the Henderson-Hasselbalch equation
 Starting with an acid

 Starting with base

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Titration of weak acids & weak bases with
strong titrant
At equivalence point
 All sample is converted to its conjugate form
 If the sample was an acid-solve the pH using KB
relationship
 If the sample was a base-solve the pH using KA
relationship

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Titration of weak acids & weak bases with
strong titrant
Overtitration:

 Identical to strong acid/strong base example.

 Need to account for the amount of excess titrant & how

much it has been diluted.

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Titration of weak acids & weak bases with
strong titrant
 Eg. 100 mL solution of 0.1 M benzoic acid is titrated with
0.1 M NaOH. Construct a titration curve.

For benzoic acid

Ka=6.31 x 10-5
pKa=4.20

1) Volume of NaOH needed to reach eq. point

Moles C5H6COOH = moles NaOH
VNaOH = 100.0 mL

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Titration of weak acids & weak bases with
strong titrant
2) Before titration:

 Assume [A-] is negligible compared to [HA]

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Titration of weak acids & weak bases with
strong titrant

2) Before titration:

0.0025 M

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 Titration of weak acids & weak bases with
strong titrant
3) After addition of 10mL NaOH
Henderson-Hasselbalch equation
pH = pKa + log [C5H6COO-]
[C5H6COOH]

[C5H6COOH] = moles unreacted C5H6COOH = MVC5H6COOH- MVNaOH

Vtotal Vtotal
= (0.1M)(100mL)-(0.1M)(10mL)
110 mL
= 0.082M
[C5H6COO ] = moles NaOH added = MVNaOH
-

Vtotal Vtotal
= (0.1M)(10mL)
110 mL
= 0.009M
pH = 4.2 + log (0.009/0.082) = 3.24

 Calculate other point by repeating this process

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Titration of weak acids & weak bases
with strong titrant
mL titrant

Note:
50mL titrant
pH = pKA

Also, there was only a

change of 1.91 in the
pH from 10mL to 90mL
titrant.

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Titration of weak acids & weak bases with
strong titrant

mL titrant

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Titration of weak acids & weak bases with
strong titrant
4) At equivalence point
 100mL titrant:
 All acid has been converted to its conjugate base –
benzoate
 Use KB relationship.

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Titration of weak acids & weak bases with
strong titrant
4) At equivalence point
n benzoic acid = n NaOH
 Predominate ion in solution is A-, which is a weak base

[A-] = moles acid/ total volume = 0.05M

 We have diluted the sample & the total volume at this point
is 200 mL.
 We can assume that [benzoic acid] is negligible compared
to [benzoate].

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Titration of weak acids & weak bases with
strong titrant
4) At equivalence point
C5H6COO- (aq) + H2O (l) OH- (aq) + C5H6COOH

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Titration of weak acids or weak
bases with strong titrant

mL titrant

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Titration of weak acids or weak bases with
strong titrant
5) Overtitration
 Need to account for the dilution of titrant.
 Eg: 10 mL excess.

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Titration of weak acids or weak bases with
strong titrant

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Titration of weak acids or weak bases with
strong titrant

mL titrant

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Titrations of Polyprotic Acids
When one titrates
a polyprotic acid
with a base there
is an equivalence
point for each
dissociation.

Titration curve for the reaction of

50.0 mL of 0.10 M H3PO3 with
0.10 M NaOH

© 2009, Prentice-Hall, Inc.

Titrations of Polybasic Base

8-50
 Selecting & Evaluating the End Point
• The equivalence point occurs when
stoichiometrically equal amounts of analyte & titrant
react. It is, therefore, a theoretical value.

• An end point for a titration is determined experimentally

& represents the analyst’s best estimate of the
corresponding point. Any difference between the 2 values
is a source of determinate error.

• For most acid-base titrations, the inflection point (the

greatest slope in the titration curve) very nearly coincides
with the equivalence point.

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 Selecting & Evaluating the End Point
• The main limitation to use a
titration curve to locate the pKa = 11
equivalence point is that an
inflection point must be pKa = 9
present. pKa = 7
• Sometimes, an inflection

pH
pKa = 5
point may be missing or
difficult to detect due to the pKa = 3
small value of acid pKa = 1
dissociation const., Ka.
Vol. of titrant
• The figure shows the titration curve for a weak acid with
a strong base titrant. The inflection point is visible for Ka
larger than 109, but is missing when Ka is 1011.

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 Selecting & Evaluating the End Point
- Another situation where an inflection point is missing
or difficult to detect occurs when the analyte is a
multiprotic weak acid or base whose successive
dissociation const. are similar in magnitude.

Maleic acid
Malonic acid
pH

pH
Ka1 = 20000 Ka2 Ka1 = 690 Ka2
pKa1 = 1.91 pKa1 = 2.85
pKa2 = 6.33 pKa2 = 5.70
Vol. of titrant Vol. of titrant
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 Selecting & Evaluating the End Point

Succinic acid
pH Ka1 = 27 Ka2
pKa1 = 4.21
pKa2 = 5.64
Vol. of titrant

• In general, inflection points are distinct when

successive Ka differs by a factor of at least 500 (or
pKa of at least 2.7)

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 Indicators
Acid-base indicators are highly colored weak acids or
bases.
HIndic Indic + H+
color 1 color 2
They may have more than one color transition – methyl
red (yellow to orange to red)

One of the form may be colorless –

phenolphthalein (colorless to purple)

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 Indicators
• During an acid-base titration, the indicator acts as an
additional weak acid or base.
• It must be weaker than the species being determined.
• It must be present at relatively low concentrations so as
not to interfere with the normal titration curve and
equivalent point.
• It must give a sharp and distinct color change.

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Indicators

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 Indicators

Selection of an Indicator:
• The smallest possible amount that can produce a color
that we can observe should be used.

• The Indicator should not significantly start to undergo a

color change until we have passed the equivalent point.

• The average analyst will observe a color change when

about 1/10 of the indicator be converted.

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 Indicators
• The pH for conversion of approximately 1/10 of the
indicator:
if starting from basic conditions :

if starting from acidic conditions :

• Under these conditions, the transition range for the

indicator is pKA  1.

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 Indicators

• Ideally then, we want our indicator’s pKa to be one unit

above the pKa for the acid sample.

• For bases, it should be one unit lower.

• We seldom find a `perfect` indicator so we should use

one that is a minimum of one unit away.

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 Indicators
Indicator Acid Color Base Color pH Range
Cresol red red yellow 0.2 – 1.8
Methyl orange red orange 3.1 – 4.4
Bromocresol green yellow blue 3.8 – 5.4
Methyl red red yellow 4.2 – 6.3
Litmus red blue 5.0 – 8.0
Bromothymol blue yellow blue 6.0 – 7.6
Cresol red yellow red 7.2 – 8.8
Phenolphthalein colorless purple 8.3 –10.0
Alizarin yellow Ryellow orange/red 10.1–12.0

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 Indicators
• In some cases, mixed indicators or by adding a neutral
screening dye to an indicator give a narrower range of
pHs over which the color change occurs.

Mixed Indicator Acid Color Base Color pH Range

Bromocresol green & methyl orange orange blue-green 3.5 – 4.3
Bromothymol blue & phenol red yellow violet 7.2 – 7.6

Screened Indicator Acid Color Base Color pH Range

Dimethyl yellow & methylene blue blue-violet green 3.2 – 3.4
Methyl red & methylene blue red-violet green 5.2 – 5.6
Neutral red & methylene blue violet-blue green 6.8 – 7.3

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 Indicators
• To minimize the determinate error, an indicator’s entire
color transition must lie within the sharp transition in pH
occurring near the equivalence point.

Example: Phenolphthalein is
an appropriate indicator for
the titration of 0.1M acetic
acid with 0.1M NaOH.
Bromothymol blue is

pH
inappropriate since its change
in color begins before the
initial sharp rise in pH and, as
a result, spans a relatively
large range of volumes. Vol. of titrant

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http://www.youtube.com/watch?v=6Y4Y-__ME60
 Titration Errors
Determinate error – excess titrant must be added to the
sample to convert the indicator.
The effect can be minimized by titration of one or more
blank samples:
• Same solution volume
• Identical amount of indicator

The blank amount can then be subtracted from the total

amount of titrant needed.

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 Titration Errors
Indeterminate Errors
• Each person will differ in how well they can observe a
specific color change.

• Running a blank will help minimize problems.

• We can also prepare a reference solution – a blank adjust

to the exact pH for the desired end point (pKA indicator
– 1)

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 Finding the End Point
Besides using visual indicator, end point can also be
determined by:

• Autotitrator
- pH is measured by electrodes immersed in the analyte solution.

 pH / V and (pH / V) / V are computed.

- end point  when pH / V is maximum; (1st Derivative) and

(pH / V) / V = 0 (2nd Derivative)

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Finding the End Point

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 Quantitative Applications
Inorganic Analysis:
Inorganic acids & bases too weak to be analyzed by an
aqueous acid-base titration can be analyzed by adjusting the
solvent or by an indirect analysis.
Eg. Titrating boric acid, H3BO3, with NaOH is limited by
boric acid’s small KA (5.8  1010).
KA increases to 1.5  104 when mannitol is added to the
solution. Thus results in a sharper end point & a more accurate
titration.
Acid-base titrimetry -- standard method for the determination
of alkalinity, acidity, & free CO2 in water & wastewater
analysis.

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 Quantitative Applications
Organic Analysis:
Kjeldahl Method to determine the protein in a sample:
• The sample is digested with HgO as a catalyst, K 2SO4, &
conc. H2SO4 (to convert N to NH4+).
• The solution is boiled until it turns clear, & for another 30
minutes.
• After cooling, water and 4% w/v K2S are added to remove
the HgO catalyst.
• Then add NaOH to convert NH4+ to NH3.

• Distill the NH3 into a collecting flask containing a known

amount of standardized HCl.
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 Quantitative Applications
Kjeldahl Method (cont.)
• After distillation is complete, titrate the excess HCl with a
standard solution of NaOH, using methyl red as a visual
indicator.
• The analysis for proteins is based on a determination of
the % w/w N in the sample.
 Different proteins have different amounts of N, the
experimentally determined % w/w N is multiplied by
a factor to give the % w/w protein in the sample.
 5.7g of cereal protein for every g of N
 6.25g of meat protein for every g of N
 6.38g of dairy products protein for every g of N
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Example

A 0.7121 g sample of a wheat flour was analyzed by the

Kjeldahl method. The ammonia formed by addition of
concentrated base after digestion with H2SO4 was distilled
into 25 mL of 0.04977 M HCl. The excess HCl was then
back titrated with 3.97 mL of 0.04012 M NaOH.
Calculate the percent protein in the flour.

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Solution
 Amount HCl
= 25 mL HCl x 0.04977 mmol HCl/mL HCl
= 1.2443 mmol
 Amount NaOH

=3.97 mL NaOH x 0.04012 M mmol NaOH/mL NaOH

=0.1593 mmol
 Amount N = 1.0850 mmol

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Exercise
 The amount of protein in a sample of cheese is
determined by a Kjeldahl analysis for nitrogen.
After digesting a 0.9814g sample of cheese, the
nitrogen is oxidized to NH4+, converted to NH3 with
NaOH, and distilled into a collection flask
containing 50.00 mL of 0.1047 M HCl. The excess
HCl is then back titrated with 0.1183 M NaOH,
requiring 22.84 mL to reach the bromothymol blue
end point. Report the %w/w protein in the cheese
given that there is 6.38 g of protein for every gram
of nitrogen in most dairy products.

Answer: 23.1 % w/w protein

 Evaluation of Acid-Base Titrimetry
Scale of operation:
• The volume of titrant needed to reach the equivalence
point is proportional to the absolute amount of analyte
present in the solution.
• In solution, the smallest conc. of analyte that can be
analyzed is approximately 103 M.
• Methods for titrations on a much smaller scale have
been developed. The smallest volume successfully
titrated was 20 L.

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 Evaluation of Acid-Base Titrimetry
Accuracy:
• Relative errors of 0.1 – 0.2%.
• The main limitation -- the difference between the end
point and the equivalence point.

Precision:
• Depends on the precision with which the end point
volume can be measured & the precision of the end
point signal.
• Under optimum conditions, a relative precision of 0.1%
- 0.2% can be accomplished.

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 Evaluation of Acid-Base Titrimetry
Sensitivity:
• The sensitivity can be increased by decreasing the conc.
of the titrant, or for polyprotic, to titrate to a later
equivalent point.

Selectivity:
• Acid-base titrants are not selective, as a strong acid/base
titrant will neutralize any base/acid, regardless of
strength. The relative acid or base strength of the analyte
& the interferent, therefore, determines selectivity.

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 Evaluation of Acid-Base Titrimetry
Time, Cost, & Equipment:

• Acid-base titration require less time than most gravimetric

methods, but more time than many instrumental methods of
analysis, particularly when analyzing many samples.

• With the availability of instruments for automated titrations,

analysis time becomes less of a problem.

• For titration manually, the equipment (buret & possibly a

pH meter) are inexpensive & easy to maintain. Instruments
for automatic titrations are more expensive.

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