Application of
Neutralization Titrations
Reagents for Neutralization Titrations
Neutralization Titrations acid/base
titrations
Strong acids and bases are used
Reason: sharper endpoints (more
pronounced)
Preparation of standard acid solutions
Prepared by diluting an approximate
volume of conc reagent then
standardized
Less frequently: density measurements
(Available data: conc. vs density)
HCl
widely used for titration of bases
Stable indefinitely
Do not cause troublesome pptn rxns with most
cations
Reported that 0.1 M HCl soln can be boiled for 1 hr
with loss of acid; 0.5 M for 10 minutes
Stock solution of HCl
Prepared by dilution of a quantity of conc acid with a
known volume of water then distilled
Final quarter of distillate is clled the constant boiling HCl
Has fixed and known composition,, dependent only on
pressure
For P of 670-780 torr:
Stds solns are then prepared by diluting weighed this
acid to known volumes
HClO4 and H2SO4 are stable and used
for titration when Cl interferes by
forming pptes
HNO3 is seldom used because of its
oxidizing properties
Standardization of acids
Sodium Carbonate
Frequently used
PS grade is available commercially
Can be obtained by heating to 270
300oC for 1 hr
Has two endpoints
1st: at pH 8.3 - to
2nd: at pH 3.8 - to
Boiled to eliminate carbonic acid to
destroy buffering effect
Titration is resumed after cooling
yielding to sharper endpoints
Tris-(hydroxymethyl)aminomethane
(TRIS or THAM)
Rxn:
Greater mass/mole of proton
Na2B4O7H2O
Rxn
Prepation of Std Solns of Base
NaOH is the most common base
KOH or Ba(OH)2 is also used
None has PS purity, so standardization is
reqd
Effect of CO2 on Basic Solutions
Bases rapidly reacts with atmospheric
solutions to produce carbonates:
When using a acid-range indicator (eg
bcg or mo), no error occurs during
analyses since
But indicators used are usually are base-range,
resulting to carbonate error:
To eliminate:
use same indicator in analysis and standardization,
though less sharp endpoints
Steps are also taken to remove carbonate ions b4
standardization
For conc base solutions, Na2CO3 has low solubility;
solids are removed by decantation or vacuum
filtration
Water must be free of CO2, should be boiled then
cooled (hot alkali soln absorb CO2 rapidly)
Deionized water is safer to use
Use of tightly capped PE bottle (short term only)
Do not use glass bottles (loss of 0.1 to 0.3%/wk,
freezing)
Standardization of Bases
Potassium Hydrogen Phthalate
(KHP, KHC8H4O4, [204.2])
An ideal PS, can be used without purification
Benzoic Acid (C6H5COOH)
Can be obtained in high purity
Has limited solubility on water
Dissolved in ethanol before dilution in water
Potassium hydrogen iodate
High MW/mol H+
A strong acid
Can be titrated with any indicator with a
transition range b/n a pH of 4-10
Application
Elemental analysis
Kjeldahl Method determination of
organic nitrogen
Sample is decomposed in hot sulfuric acid (1
hr), and ammonia produced is condensed
and titrated with acid
Converts amino and amide groups to NH3,
but not nito, azo or azoxy groups and certain
aromatic heterocyclic compounds eg
pyridine
%protein = f*%N; f=6.25 for meats, 6.38 for
dairy, and 5.70 for cereal
Sulfur
Found in organic and biological materials
Sample is burned in a stream of oxygen
(SO2, SO3)
Collected in dilute H2O2:
H2SO4 is then ttd with std base
Other non-metallic elements
determination is listed in Table 16-1
Determination of Inorganic Substances
Ammonium Salts
Kjeldahl method can be used
Nitrates and Nitrites
Reduced first to NH4+ by Devardas (50%Cu,
45%Al, 5%Zn) or Arnds (60%Cu, 40%Mg) alloy
Then proceed Kjeldahl method
Carbonate and Carbonate Mixture
Compatible combinations of NaOH, NaHCO 3,
Na2CO3
No more than two of these three constituents
can exist in appreciable amount in solution
because rxn eliminates the third
NaOH + NaHCO3 Na2CO3 +H2O
If NaOH is used up, NaHCO3 and Na2CO3 are
present
If NaHCO3 is used up, NaOH and Na2CO3 are
present
if equimolar are used, only and Na2CO3 is
present
Using different indicators (acid- or baserange)
Titration Curves of Compatible Mixtures
1st endpoint:
2nd endpoint:
(2 sources)
Organic Functional Groups
Carboxylic and sulfonic acids readily
titratable with base using base-range
indicator
Amines titrated with strong bases for
aliphatic; for aromatic and cyclic amines
are tirated in non-aqueous ie anhydrous
acetic acid to enhance basisity
Esters - treated with excess base
(saponification), then backtitrated with
std acid
Alcohols can be determined by
esterification (rxn of acetic or phthalic
anhydrides with ROH in pyridine);
Carbonyl compounds
Aldehydes and ketones
Reacted with hydroxylamine
hydrochloride:
Liberated HCl is titrated with a base
Problems
