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Bronsted_Lowery_s_1628555744
Bronsted_Lowery_s_1628555744
B + HA HB+ + A-
Base proton Acid Acid Base Proton
Receiver Proton source Proton source Receiver
Equilibrium Constant Ka and Kb
The Equilibrium Constant for a Brønsted acid is
represented by Ka, and base is represented by Kb.
[H3O+][CH3COO–]
Notice that H2O is not Ka = –––––––––––––––––
included in either [CH3COOH]
equilibrium expression.
[NH4+] [OH–]
Kb = –––––––––––––
[NH3]
pH of 1M ACOH =2.4
Solvent Selection for NAT
Solvents, which are used is non-aqueous solvent,
and plays major role in NAT analysis.
Classified as four types:
1. Aprotic solvents: Chemically neutral
2. Protogenic solvents: Acidic nature readily donate
protons.
3. Amphiprotic solvent: Which are slightly ionize
and donate and accept protons.
4. Protophilc solvents: Posses high affinity for
protons.
Aprotic Solvents
Aprotic Solvents:
◦ Solvents are Chemically Neutral,
◦ Un-reactive under the titration conditions; do not
undergo reactions with acids and bases
◦ They possess low dielectric constants.
◦ Do not cause ionization in solutes and
◦ Aprotic solvents are frequently used to dilute the
reaction mixture and enhance the end point.
Eg. Toluene, carbon tetrachloride , acetonitrile,
benzene, and chlorinated hydrocarbons
Protogenic Solvents
Protogenic Solvents: ( Protogenic – Proton producing)
DMF:
Benzoic acid, amides etc
Titrants for NAT
Choice of Titrants:
Basic compound:
A volumetric solution of perchloric acid in glacial acetic
acid is preferred, or perchloric acid in dioxane is used as
required.
Acidic compound:
A volumetric solution of sodium methoxide or Lithium
methoxide in a mixture of methanol and toluene
tetra-n-butylammonium hydroxide and trimethyl
hexadecyla mmonium hydroxide (in benzene-methanol
or isopropyl alcohol),
USP Titrimetry <541>
Systems for Nonaqueous Titrations
Type of Acidic (for titration of bases Relatively Neutral Basic (for titration of Relatively Neutral (for
Solvent and their salts) (for differential titration acids) differential titration of
of bases) acids)
Solvent # Glacial Acetic Acid Acetonitrile Dimethylformamide Acetone
Acetic Anhydride Alcohols n-Butylamine Acetonitrile
Formic Acid Chloroform Pyridine Methyl Ethyl Ketone
Propionic Acid Benzene Ethylenediamine Methyl Isobutyl Ketone
(II) − pM)
Oxidation- Platinum E = E° + Calomel or Titrations with arsenite, bromine,
Reduction (0.0591/n) × silver–silver cerate, dichromate, nitrite,
log [ox]/[red] chloride exacyonoferrate(III), iodate,
permanganate, thiosulfate
(1) Appropriateform of Nernst equation describing the indicating electrode system: k = glass
electrode constant; k′ = constant derived from Hg–Hg(II)–EDTA equilibrium; M = any metal
undergoing EDTA titration;
[ox] and [red] from the equation,ox + ne ⇄ red.
(2) Listing is representative but not exhaustive. Reproduced From USP
Pontentiomertic Titration
Potentiometric titration :
The end-point of the titration is determined by
variation of the potential difference between 2
electrodes in the solution to be examined as a
function of the quantity of titrant added.
Determine the volume consumed between the 2
points of inflexion.
Electrode :
Selection of appropriate Electrode is important to
determine the accurate determination
Preferred electrode for acid-base titrations is glass-
calomel or glass- silver-silver chloride electrode ,
unless otherwise specified in Pharmacopeia
Typical Titration Graph
Preparation of 0.1N Perchloric Acid
Preparation of 0.1N Perchloric Acid in Glacial Acetic Acid:
Mix 8.5 ml 70% of perchloric acid with 500 ml of
glacial acetic acid and 21 ml of acetic anhydride,
cool, and add glacial acetic acid to make 1000 ml.
Allow the prepared solution to stand for 1 day for
the excess acetic anhydride to be combined, and
determine the water content 0.02% and 0.5% (if >
0.5%, add acetic anhydride).
Perchloric Acid Preparation
Perchloric acid (70 to 72%) addition in solvent
contain water is exothermic and may decompose,
handle carefully.
Conversion of acetic anhydride to acetic acid
requires 15-45 min
Allow to cool to room temperature before adding
glacial acetic acid
Avoid adding an excess of acetic anhydride
especially when primary and secondary amines are
to be assayed, because it may react and convert
acetylation .
Standardization of Perchloric Acid
4. Filter the solution in sintered glass filter and rinse with of 50ml dry
toluene repeat 2 or 3 times.
5. Add washing toluene into filtrate ( step-3) and dilute to 1000ml with
anhydrous Toluene and mix.
Filling of electrolyte:
◦ Remove the aqueous KCl completely
◦ Rinsing with water if any residual KCl
◦ Rinsing with the non-aqueous solvent to remove water
◦ Fill the electrode with the suitable electrolyte.
Precautions to Minimize the Error
Stirring rate should be adequate. As a general rule, it should be
as high as possible. But avoid the formation of a vortex during
stirring.
If endpoint recognition criteria (ERC) is too small can result in
an incorrect equivalence point
Use the titration parameters “signal drift” and “min./max.
waiting time” to adjust the titration rate.
Sensor is suitable for the titration. If sensors is old or dirty, it
can result in longer response times.
Check that the anti-diffusion tip is functioning correctly.
The titrant should not be stirred directly onto the electrode,
but rather away from it.
Precautions to Minimize the Error
Selection of appropriate Electrode and Electrolyte filled
shall be appropriate.
Burette tip / Diaphragm shall be free from clogging
Titration vassal shall be closed while titration
Avoid expose to atmospheric air, CO2 may interfere
Titration vassal shall not contain water or previous
residue
Sample shall be completely transferred and dissolved
No Air bubbles in the dosing cylinder and/or in the
tubing
Air bubbles in the measuring vessel and/or on the sensor
during photometric titrations
Blank Correction
Blank correction is usually obtained by residual blank
titration. Repeated in every detail except that the
substance being assayed is omitted.
An appropriate blank correction shall be included in
calculation
Difference between the volume consumed in the
residual blank titration and volume consumed for same
titration
If blank is high or suspected, repeat the analysis
Calculation
o Normality: Eq.wt/1000ml or meq/mL
o Morality: Mole/1000ml
o V1 N1 = V2N2
o N1 = V2N2/V1
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