ACID-BASE TITRATIONS

(NEUTRALIZATION REACTIONS)

APPLICATIONS
 Direct Titration Methods
1. Determination of Acids & Bases
Strong acids are titrated with standard alkaline: MO or Ph.Ph.
Weak acids are titrated with standard alkaline: Ph. Ph. not M.O.
Acids which are insoluble in water (as benzoic acid) should be first dissolve in
neutralized ethanol and then titrated with NaOH: Ph. Ph.
Acid salts (KH-phthalate, KHSO4 & KH-tartarate) are titrated with NaOH: Ph.Ph.
Boric acid as a weak monobasic acid (K2 = 5.8  1010-), is titrated with
standard NaOH after addition of polyhydroxy compounds (e.g. glycerol): Ph.Ph.

CH2 OH OH CH2 OH
CH OH + B CH O
B O H + H2O
CH2 OH OH OH CH2 O

Strong base are titrated with standard acid: MO or Ph.Ph.

Weak bases are titrated with standard acid: Ph. Ph. not M.O.
2. Double-Indicator Titrations
 Direct titration of a mixture of two monobasic acids to determine the quantity of
each acid by the use of two indicators.
 The difference in the ionization constants of the two acids must be at least 104.
Thus, it is possible to titrate HCl in the presence of boric acid (Ka = 5.5 1010 )
or HCl in the presence of acetic acid (Ka = 1.8 105 ).

 H+ of HCl  ionization of HOAC

by common ion effect;
NaOH neutralizes HCl first.
After completion of the reaction,
NaOH neutralizes AOAC.
3. Titration of Easily Hydrolysable Salts (Displacement Titration)
These salts are formed from:
– A strong base & a very weak acid (KCN, borax & Na2CO3).
– Strong acid & a very weak base (FeCl3 & AlCl3).
a. Titration of Potassium Cyanide
KCN + H2O  HCN + K+ + OH
K+ + OH  H2O
The net reaction: KCN + HCl  HCN + KCl

b. Titration of Borax (Na2B4O7)

Na2B4O7 + 7 H2O  2 NaOH + 4 H3BO3
2 NaOH + 2 HCl  2 NaCl + 2 H2O ( M.O. )

glycerol
4H3BO3 + 4NaOH 4NaBO2 + 8H2O ( Ph.Ph )

Titration of a Mixture of Borax & Boric Acid ?.

b. Titration of Sodium Carbonate (Na2CO3)
Na2CO3 + HCl  NaHCO3 + NaCl pH = 8.35 Ph. Ph. K1= 4.2107
NaHCO3 + HCl  CO2 + H2O + NaCl pH = 3.8 M.0. K2 = 4.8  1011

Boiled solution

Kb1  106 (required for a sharp E.P.),

the pH break is decreased by the
formation of CO2, beyond the first E.P.

Kb2  106 : the second E.P. is not very

sharp. It can be sharpened by boiling
off the CO2 .

– Titration of a Mixture of Na2CO3 & NaHCO3 ?.

– Titration of a Mixture of Na2CO3 & NaOH ?.
– Titration of a Mixture of Na2CO3 & Na2B4O7 ?.
4. Biphasic Titrations
This method is applied for water–soluble salts of water–insoluble acids
(but soluble in other immiscible solvents): Titration of sodium salicylate.
COO Na COO H
OH OH

+ HCl + N aC l

The liberated salicylic acid is so strong to give

an acidic pH and thus affect the indicator.
It is removed from the aqueous reaction
medium by its solubility in ether (250 times
greater than in water).
The titration with standard acid is carried out
in a separating funnel using bromophenol
blue: blue to pale green.
 Indirect (Back or Residual) Titration Methods

Used when direct titration is not suitable as in:

– Volatile substance as ammonia or formic acid (loss).
– Substance, which require heating with standard reagent.
– Insoluble substance as ZnO, CaO, and BaCO3.
– Substance needed excess reagent for rapid quantitative reaction (lactic acid).

Carried out as follow:

A known excess standard solution is first added and allowed to react completely
with the sample. The residual quantity of the added standard is then determined.