UNIT 8

Acid-Base Titration maidliu 05.02.2019

 Acid-Base Titration
• It is a method of quantitative analysis for
determining the concentration of an acid/base by
neutralizing it with standard solution of
base/acid.

Types of acid-base titration

1. Alkalimetry: determination of basic content in a
sample by titrating it with a standard acid
solution
2. Acidimetry: Determination of acid content in a
sample by titrating it with a standard base
solution
 Titration Curve
• The course of an acid-base titration is best followed by
examining the pH as the titration progresses.

• A titration curve
provides visual picture
of how the property of
the titration reaction
changes as the titrant is
added to the analyte.
• It helps choose the
proper titrants and
indicators to be used for
the analysis
 Determining the Equivalence point
• Equivalence points in acid-base titrations are
determined most often using chemical
indicators that change color at or near
equivalence point.
• Acid-base indicators are weak organic acids or
bases whose conjugate forms have different
colors.
• It must be weaker than the analyte acid or
base so that it reacts last with the titrant.
 Determining the Equivalence point
Equilibrium for Indicator
• The behavior of an acid-type indicator:
HIn + H2O ↔ H3O+ + In—
(acid color) (base color)

• The behavior of an base-type indicator:

In + H2O ↔ OH— + InH+
(base color) (acid color)
 Determining the Equivalence point
Acid-Base Indicator
• Human eye is not sensitive to color difference in a
solution containing a mixture of HIn and In— .

• An average observer visualizes color imparted by a

typical indicator within concentration ratio:
[Hin]/[In—] = 10 – 0.1

• This ratio vary considerably from indicator to indicator.

Indicator pH range = pKa ± 1
 Determining the Equivalence point
Acid-Base Indicator

Diagram showing the relationship

between pH and an indicator’s color.
 Determining the Equivalence point
• The inflection point (the
point in titration having
the greatest slope) very
nearly coincides with the
equivalence point.

• To minimize titration error,

an indicator’s entire
transition pH range must
fall within the rapid
change in pH at the
equivalence point.
 Reagents for Acid/Base Titrations
• Standard Solutions (Titrant)
– Use of strong acids or strong bases
– React more completely with an analyte, yielding a
sharper endpoint
• Primary Standards
• Acid/Base Indicators
 Acid Titrants
1. Hydrochloric acid , HCl
• Widely used for titration of bases
• It is a strong acid; dilute solutions are stable with
little or reducing power; chloride ion does not
form precipitates with most cations
• Concentrated acid is not a primary standard
2. Perchloric acid, HClO4
3. Sulfuric acid, H2SO4
• HSO4— is a weak acid
• Forms insoluble sulfates with a number of
common cations
 Primary Standard Bases
Primary standard bases are used for
standardization of acids.
1. Sodium carbonate, Na2CO3
– Most often used for the standardization of acid
solutions
– High purity solid are commercially available, but it
is hygroscopic

Na2CO3 + 2H3O+ → H2CO3 + 2Na+ + 2H2O

 Primary Standard Bases
There are two endpoints observed in the titration of
Na2CO3.

• Conversion of CO3—2 to
HCO3—, pH 8.3
• Formation of CO2
– The second endpoint is
used for the
standardization bec
change in pH is greater
than the first.
 Primary Standard Bases
2. Sodium tetraborate, Na2B4O7•10H2O
• Also known as borax; it has high molar mass
• Cannot be heated to remove water
• Stored in dessicator over an aqueous solution
saturated with NaCl and sucrose (ensures no
dehydration to occur)
Na2B4O7 + 2H3O+ + 3H2O → 2Na+ + 4H3BO3
 Primary Standard Bases
3. Tris(hydroxymethyl)aminomethane,
(HOCH2)2CNH2
• TRIS or THAM, available in primary-standard
purity
• Substantially greater MM/mole of protons
consumed
(HOCH2)2CNH2 + H3O+ → (HOCH2)2CNH3+ + H2O
 Problem Set
1. A 0.4512g of primary standard grade Na2CO3
(105.99 g/mol) required 36.44mL of an HCl
solution to reach the endpoint in the reaction.
What is the molarity of the HCl?

Answer: 0.2336M HCl

 Problem Set
2. Titration of a 0.7439-g sample of impure
Na2B4O7 required 31.64mL 0.1081M HCl.
Express the results in terms of percent:
(a)Na2B4O7 and (b) B2O3.

Answer: 46.25% Na2B4O7, 32.01% B2O3

 Base Titrant
Sodium hydroxide, NaOH
– Used almost exclusively for titrating acids in
solutions
– Primary-standard-grade purity is not available
– Dilute NaOH solutions are stable can be stored in
plastic containers.
– It slowly reacts with glass to form soluble silicates.
– Has a cementing property; often glass stoppers
are “freeze” tightly to the mouth of the container.
– It must be protected from carbon dioxide
CO2(g) + 2OH— → CO32— + H2O
 Primary Standard Acids
2. Benzoic acid, C6H5COOH
– Available in sufficient purity
– Not very soluble in water; most often mixed with
water-alcohol and non-aqueous solvents
C6H5COOH + OH— → C6H5COO— + H2O
3. Potassium hydrogen iodate, KH(IO3)2
– Strong acid that can be titrated using any
indicator with transition range between pH 4-10
KH(IO3)2 + OH— → K+ + 2IO3— + H2O
 Problem Set
3. A 300.0-mg sample containing H3PO4 and inert
material was diluted with water and titrated with
0.05000M NaOH. The endpoint was reached after
29.00mL of the titrant was added. Calculate the %
H3PO4 in the sample.
H3PO4 + NaOH → Na2HPO4 + 2H2O

Answer: 23.68% H3PO4

 Acid-Base Indicators
1. Phthalein indicators
– Phenolphthalein is the best known indicator in this
group.
– Indicator transition range: pH 8.0-9.8
– Acid form (colorless) – Base form (red)
– Not soluble in water; usually prepared in ethanol

Equilibrium of acid-
base forms of
phenolphthalein
 Acid-Base Indicators
2. Azo indicators
– Exhibit color change from red to yellow
– Methyl red , pH 4.2-6.2
– Methyl orange, pH 3.1- 4.4

Equilibrium of acid-base forms of methyl orange

Assignment
Skoog
10-9 a-c
10-11 b,c
10-14
10-15