MODULE 6:

Alkalimetric
Analysis
Alkalimetry
• Analogous to acidimetry, but the samples or
substances under observation are acids. • The
acid, acid salt or other acidic substance is
directly titrated with a standard alkali solution,
or added with an excess of the standard alkali
solution, with the excess back titrated by a
standard acid solution.
• Most inorganic acids employ methyl red or
phenolphthalein as indicators.
• Most organic acids employ:
 – Thymol Blue: A – yellow; B - blue
– Bromothymol Blue: same with Thymol Blue
– Thymolphthalein: A – colorless; B – blue
End points can also be detected by
potentiometry.
Direct Alkalimetric Titrations: Assay of
HCl HCl + NaOH 🡪 NaCl + H2O
Sample Calculation:
In an assay procedure, 46mL of 0.9035N
NaOH was consumed in the titration of a
4.0520g sample of HCl. What is the
sample’s percent purity?
mEq: 36.45g/1/1000 🡪 0.03645g/mEq
 %P = V x N x mEq x 100
Sx wt.
= 46mL x 0.9035N x 0.03645g/mEq x
100 4.0520g
= 37.39%
Direct Alkalimetric Titrations: Assay of Diluted
H3PO4
H3PO4 + 2NaOH 🡪 Na2HPO4 + 2H2O
• This procedure employs direct titration of the sample
with a blank determination.
• A blank determination is employed for correcting the
actual amount of titrant that has reacted with the
analyte.
• In this assay, a blank determination is employed since
the indicator only changes color in a highly basic
 condition.
Sample Calculation:
• A 10mL sample of diluted H3PO4required 42.76mL of
1N NaOH. A blank determination was made and
22.35mL of 1N NaOH was consumed to the appearance
of a blue color. Calculate the % of H3PO4in the sample.
Assay of Diluted H3PO4
mEq = 97.97g/2/1000 🡪 0.04899g/mEq
%P = (Va – Vb) x N x mEq x 100
Sx vol.

%P = (42.76mL – 22.35mL) x 1N x 0.04899g/mEq x

100 10mL
 = 10% w/v
Direct Alkalimetric Titrations: Assay of H3BO3
H3BO3 + NaOH 🡪 NaBO2 + 2H2O
• H3BO3is a very weak
monobasic/monoprotic acid.
H3BO3 H+ + BO2- + H2O

• BO2-is a strong monoprotic base, hence a

pink color develops long before addition
of titrant.

• Glycerin is added to the reaction mixture

 to complex the BO2-, preventing the
formation of pink color prior to titration
and allowing H+to react with the titrant.
Sample Calculations: Assay of H3BO3

• Two and fourteen hundredth grams of H3BO3required a total of

34.68mL of 0.9934N NaOH to the production of a
phenolphthalein end point. Calculate the %P of the sample.

mEq = 61.81g/1/1000 🡪 0.06181g/mEq

%P = 34.68mL x 0.9934N x 0.06181g/mEq x 100
2.14g

= 99.51%
Direct Alkalimetric Titrations: Assay of
 Hydroxy Compounds
• The hydroxy compound is esterified first with acetic
anhydride.
• The acetic acid produced as by-product of the reaction
is determined by standard NaOH and is taken as the
quantitative measure of the hydroxy compound.
E.g.
O
Pyridine Δ O
O CH2CH2 O CH2CH2 O

+
OH H O CO + H3C C
3C C
OH
H3C O H3C
C

• This assay procedure requires addition of water to

convert excess acetic anhydride to acetic acid so a
blank determination should be conducted for getting
the actual amount of acetic acid liberated.
Sample Calculations: Assay of Hydroxy
 Compounds
• The blank determination would consume more titrant.
O
O
H3C C O H2 2 H3C C
+ O
C OH
H3C
O

• Hence for correction purposes, the %P of the sample would

be:
%P = (Vb – Va) x N x mEq x 100
Sx wt.
E.g.
If 2.08g of phenoxyethanol required 32.59mL of 0.9891N
NaOH and 47.78mL of the same standard solution was
required to produce a phenolphthalein end point to a blank
solution. Calculate the percent purity.

Assay of Hydroxy Compounds

mEq = 138.08g/1/1000 🡪 0.13808g/mEq

%P = (47.78mL – 32.59mL) x 0.9891N x 0.13808g/mEq x

100 2.08g

= 99.74%
Direct Alkalimetric Titrations: Assay of
H2C4H4O6
H2C4H4O6 + 2NaOH 🡪 Na2C4H4O6 + 2H2O

Sample Calculation:
A 2.00g sample of H2C4H4O6 was assayed
 alkalimetrically with 1.2247N NaOH and was
found to be equivalent to 21.71mL of the
standard solution. What is the sample’s
percent purity?
mEq = 150.04g/2/1000 🡪 0.07502g/mEq

%P = 21.71mL x 1.2247N x 0.07502g/mEq x

100 2g
= 99.73%
Other Notes on Assay of Organic Acids Using
Standard NaOH
• Phenolphthalein is the most suitable indicator
in the assay of organic acids.
 • 1N or 0.1N NaOH maybe used for such
procedures.

• Other samples that can be titrated with

standard NaOH can be acid anhydrides, acid
salts, and any other substance in which the
acidic character can be enhanced or the
particular substance of interest can be
converted to an acid.
Residual Alkalimetric Titrations
• Analytes under these methods are usually
heated, solubilized or precipitated into
substances that can react with the standard
base.
 • Samples that are commonly analyzed in this
manner are esters, acid anhydrides, acid
chlorides and aldehydes.
Assay of ASA: (Residual Titration w/ Blank Det’n)
• Sample is titrated first with standard NaOH to
convert ASA to Na acetylsalicylate and
neutralize its hydrolytic products.
OC Na

OC O

OH
+ Na OH + H2O
O CO CH3 CO CH3
O

Residual Alkalimetric Titrations: Assay of ASA

• The sodium acetylsalicylate produced is treated with
an excess of the standard base to produce sodium
salicylate and sodium acetate.
 OC Na O
O
O
+ Na OH
+
C
O H3C C
Na
C
CH3Na
O O OH O

• The excess NaOH is back titrated with standard H2SO4

to a phenolphthalein endpoint.
• A blank determination is performed, where the same
amount of reagents are used and is back titrated with
standard acid, for correction and ensure reliability of
the end point.
• The difference between the volume of the acid
consumed in the blank and in the actual titration is
taken as the amount of ASA in the sample.
Sample Calculation: Assay of ASA
Sample Calculation:
Twenty 325mg-tabs of ASA where used to
make 100mL of a neutralized alcoholic
solution. 7.69mL of this solution was found
to be equivalent to 11.7mL of 0.1197N
NaOH. An additional 26.7mL of 0.1197N
NaOH was added and the excess alkali was
back titrated with 0.1184N H2SO4and
4.68mL was required to the discharge the
pink color. A blank determination was
made and 26.44mL of the standard acid
was consumed. Calculate the percent
purity and the actual weight of ASA per
 tablet.
Sample Calculation: Assay of ASA
Solve for Sx wt. first.
20tabs x 325mg = 6,500mg dissolved in 100mL
alcohol 7.69mL of this solution was used for the assay
hence:
6,500mg = __(x)mg__ 🡪 499.85mg/0.49985g
100mL 7.69mL
mEq = 180.09g/1/1000 = 0.18009g/mEq
%P = (Vb – Va) x N x mEq x 100
Sx wt.
%P = (26.44mL – 4.68mL)x 0.1184Nx0.18009g/mEq x
100 0.49985g
= 92.82%
Actual Amount of ASA per tablet:
Label Claim: 325mg x 92.82%P = 301.67mg ASA/tab