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 +¿
  2𝐻
– Frequently used 1 𝑁𝑎 2 𝐶𝑂3
¿

– 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   1𝐻
+¿
¿
(TRIS or THAM) 1 𝑇𝑅𝐼𝑆 /𝑇𝐻𝐴𝑀
• Rxn:

• Greater mass/mole of proton +¿

  𝐻
1 ¿
– Na2B4O7▪H2O 1 𝐵 4 𝑂7
2−

• 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  1 𝑂 𝐻
−

1 𝐾𝐻𝑃
(KHP, KHC8H4O4, [204.2])
• An ideal PS, can be used without purification
– Benzoic Acid (C6H5COOH)   1 𝑂 𝐻−
• Can be obtained in high purity 1 𝐵𝑒𝑛𝑧𝑜𝑖𝑐 𝐴𝑐𝑖𝑑

• Has limited solubility on water

• Dissolved in ethanol before dilution in water
– Potassium hydrogen iodate −
  1𝑂𝐻
• High MW/mol H+
1 𝐾𝐻 ( 𝐼𝑂 3 )
• 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
• Coverts 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 Devarda’s (50%Cu, 45%Al,
5%Zn) or Arnd’s (60%Cu, 40%Mg) alloy
– Then proceed Kjeldahl method
• Carbonate and Carbonate Mixture
– Compatible combinations of NaOH, NaHCO3, 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 base-range)
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); excess anhydride is hydrolize to give
acetic acid; acetic acid is titrated with alcoholic
NaOH/KOH, then compared to blank
• Carbonyl compounds
– Aldehydes and ketones
– Reacted with hydroxylamine hydrochloride:

– Liberated HCl is titrated with a base

Problems