Neutralization Titration

(Acid/base titration)

Dr. Mohammad Khanfar

 Acid/Base Titration
• Standard Solutions
• The standard solutions used in neutralization titrations are
strong acids or strong bases because these substances react
more completely with an analyte than do their weaker
counterparts, and they therefore provide sharper end points.
• HCI, HCIO4, H2S04, NaOH, and KOH.
 Acid/Base Titration
• Acid/Base Indicators
• Many substances, both naturally occurring and synthetic,
display colors that depend on the pH of the solutions in
which they are dissolved.
• An acid/base indicator is a weak organic acid or a weak
organic base whose undissociated form differs in color from
its conjugate base or its conjugate acid form.
• Indicator pH range = pKa ± 1
• Indicator should fall within the range of inflection of the
strong acid/strong base titration curve.
 Acid/Base Titration
• Internal structural changes accompany dissociation and cause
the color change
Acid/Base Titration

Methyl orange, pKa 3.7

 Titration Of Strong Acids And Strong Bases

• Consider the titration of 50 ml of 0.05 M HCl (analyte) with 0.1M NaOH

(titrant).
HCl + NaOH NaCl + H2O

• First we determine equivalent point

• M1V1 = M2V2
• V = 25ml
• Initial Point
• Before any base is added, the solution is 0.0500 M in H30+, and
pH = -log[H30+] = -log 0.0500 = 1.30
• After Addition of 10.00 mL of Reagent
• The H+ ion concentration is decreased as a result of both reaction with the
base and dilution.
• pH = 1.6
 Titration Of Strong Acids And Strong Bases

• After Addition of 25.00 mL of Reagent (The Equivalence Point)

• At the equivalence point, neither HCl nor NaOH is in excess, and so the
concentrations of hydronium and hydroxide ions must be equal
• pH = 7
• After Addition of 25.10 mL of Reagent
• The solution now contains an excess of NaOH, pH = 10.12
 Titration Of Strong Acids And Strong Bases

• The Effect of Concentration

 Titration Of Strong Acids And Strong Bases
The Effect of Concentration

Titration curves for HCI with NaOH. Curve A: 50.00 mL of 0.0500 M HCI with
0.1000 M NaOH. Curve B: 50.00 mL of 0.000500 M HCI with 0.001000 M NaOH.
 Titrating a Strong Base with a Strong Acid

• Titration curves for strong bases are derived in an analogous

way to those for strong acids.
• Short of the equivalence point, the solution is highly basic, the
hydroxide ion concentration being numerically related to the
analytical molarity of the base.
• The solution is neutral at the equivalence point and becomes
acidic in the region beyond the equivalence point then the
hydronium ion concentration is equal to the analytical
concentration of the excess strong acid.
 Titrating a Strong Base with a Strong Acid

• Titration curves for NaOH with HCl. Curve A: 50.00 mL of O.0500 M NaOH
with 0.1000 M HCl. Curve B: 50.00 mL of 0.00500 M NaOH with 0.0100 M
HCl.
 Strong Acid/Strong Base Titration
• Calcium hydroxide (Ca(OH)2)solution
• Although this is a fairly strong alkaly and is titrated with HCl
solution, methyl orange is not used as indicator. The solution
absorbs carbon dioxide from the atmosphere to form carbonate
(pKa 7.7) but since the free Ca(OH)2 and not the total alkali content
is required, phenolphthaline is used as indicator.
 Weak acid/strong base and weak base/strong acid

• On addition of a small volume of the strong acid or strong base to a

solution of the weak base or weak acid, the pH rises or falls rapidly
to about 1 pH unit below or above the pKa value of the acid or
base. Often a water-miscible organic solvent such as ethanol is used
to dissolve the analyte prior to addition of the aqueous titrant.
• Example. Titration of 50.0 ml of 0.1 M acetic acid (pKa 4.76) with
0.1 M NaOH.
• Initial pH: calculated from [H+] = (ka. c)1/2
• pH before equivalence point: A state of equilibrium between the
acid and its conjugate base formed, and the pH is calculated from
Henderson–Hasselbalch equation
 Weak acid/strong base and weak base/strong acid

• At equivalence point: all acetic acid is consumed and

converted to sodium acetate, and pH is calculated starting
from [OH-] = (Kb. c)1/2
• pH after equivalence point: After the addition of excess
amount of NaOH, both the excess base and the acetate ion
are sources of hydroxide ion. The contribution from the
acetate ion is small, however, because the excess of strong
base represses the reaction of acetate with water.
• pH = 14 – pOH
 Weak acid/strong base and weak base/strong
acid

Curve for the titration of acetic acid with sodium hydroxide. Curve A: 0.10 M acid
with 0.1000 M base. Curve B: 0.0010 M acid with 0.0010 M base.
Weak acid/strong base and weak base/strong acid

Titration curve of 25 ml of 0.1M solution of aspirin (pKa 3.5) titrated with

0.1M NaOH
Weak acid/strong base and weak base/strong acid

Titration curve of 25 ml of 0.1M solution of quinine(pKa 8.05) titrated with

0.1M HCl
 Weak acid/strong base and weak base/strong acid

• For an acid, the measured pH when the acid is exactly half

neutralized is numerically equal to pKa. For a weak base, the
pH at half titration must be converted to pOH, which is then
equal to pKb.

• Weak acid with strong base, end point will be basic then
phenolphthalein can be used in general

• Weak base with strong acid, end point is acidic so methyl

orange can be used in general.
The effect of acid strength (dissociation constant) on titration curve .
Each curve represents the titration of 50.00 mL of 0.1000 M acid with
0.1000 M base.
The pH change in the equivalence-point region becomes smaller as the
acid becomes weaker, that is, as the reaction between the acid and
the base becomes less complete.
5-fluorouracil
A: Ureide nitrogen, very weak acidic, pKa 13
B: Ureide nitrogen, weak acid, pKa 7.0
Guanithedine
A: guanidine moiety, one of the strongest nitrogenous base pKa 11.4
B: Tertiary amine, pKa 8.3

Sulphadiazine
A: pyrimidine ring, very weak basic nitrogen , pKa < 2
B: Sulfonamide nitrogen, weak acid, pKa 6.5
C: Weakly basic aromatic amine (aniline) pKa < 2
 Weak acid/strong base and weak base/strong acid

• Blank titration
• In general, blank determinations are used if the volumetric
solution is unstable or if it alters in strength during the assay
(heating, interaction with glass, of absorption of atmospheric
CO2).
• Titration without analyte.
 Weak acid/strong base and weak base/strong acid

• Polyfunctional acids and bases

• Some acids and bases can donate or accept more than one
proton, i.e. 1 mole of analyte is equivalent to mort than one
mole of titrant. If the pKa values of any acidic or basic groups
differ by more than 4, then the compound will have more
than one inflection in its titration curve.

pKa 10.32
pKa 6.38
Weak acid/strong base and weak base/strong acid

Titration of 1 M sodium carbonate with 1M HCl

Weak acid/strong base and weak base/strong acid