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Table of Contents
NON AQUEOUS ACID BASE TITRATION ..............2 INTRODUCTION ..........................................................2 Reasons for Performing Non Aqueous Acid Base Titration ....................................................2
Interaction of H2O with the Titrant ......................2 Poor Solubility of Weak Acids (WA) or Weak Bases (WB) in H2O ...........................................................3 Explanation for a Weak Acid (WA)........................ 7
SOLVENTS USED IN NON AQUEOUS ACID BASE TITRATION ................................................................7 Protophillic Solvent ...........................................7 Protogenic Solvent ............................................8 Amphiprotic Solvents ........................................9 Aprotic Solvents ..............................................10
Reasons for using Aprotic Solvents .................... 10
THEORY OF NON AQUEOUS ACID BASE TITRATION.....10 Titration of Weak Acid (WA) ............................11
Theory ................................................................ 11 Apparatus for Controlled Environment ............. 12 Burette for protecting the Titrant ................. 12 Analytical / Titration Vessel for Analysis ....... 12 Practical Example ............................................... 12
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1. Interaction of the Titrant with H2O 2. Poor Solubility of Weakly Acidic (WA) or Weakly Basic (WB) Analyte in H2O
A Non Aqueous Acid Base Titration involves the titration by neutralization of either acid or base by their opposite entities in a non aqueous medium.
properties. As a result More titrant will be required Detected end point will give wrong result or no end point will occur
encountered during the aqueous titration of weakly acidic or weakly basic analyte by a Strong Acid or Strong Base Titrant
Figure 1: Reaction of Water with titrants in Aqueous Titration of Weak Acid or Weak Acid
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between an Acid and a Base to produce Salt and Water. E.g. Hydrochloric Acid (HCl) is neutralized by Sodium Hydroxide (NaOH) to produce Sodium
compound / Analyte
Diffe r en t Ac id B ase T h eo r y
Broadly, acid base theories are classified into 1. Arrheniuss Acid Base Theory 2. Bronsted Lowry Theory of Acid Base 3. Lewiss Theory of Acid Base
E.g. Acidity of Acetic Acid is Liquid Ammonia. 2. This theory cannot explain the acidity or basicity of ions. 3. Acidity or Basicity shown by compounds which do not donate H+ or OH-
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respectively cannot be explained by this theory. 4. This theory cannot explain the
neutralization reaction between those acids and bases where water is not produced. E.g. Neutralization of HCl by Mercuric Acetate produces
Acid HCl
Proton + H+ H+ H+ + + +
H3O+ H2PO4-
Base C5H5N
+ +
Proton H+ H+
HPO42- +
2. This theory can explain the acidity and basicity shown by same compounds. E.g. Water 4|Page
Acetic Acid 3. This theory is capable of explaining the neutralization reaction in non
E.g. H+ is a Lewis acid, since it can accept an electron to fulfill its outer shell.
H+ + e- H
A Base is a Compound / Atom / Ion capable of donating one / one pair / pairs of electron to an acid; Thus referring as Lewis Base. E.g. AlCl4- is a Lewis Base, since it can donate a pair of electrons
So, according to this theory, a neutralization reaction is a formation of Coordinate Covalent Bond between the donors and acceptors of electron pair atoms. E.g. Reaction between Boron trichloride and Triethylamine.
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(CH3COOH) than in H2O; and thus acts as a Weak Acid in Acetic Acid. It is because, H2O is more basic than that of Acetic Acid (CH3COOH) and thus can rapidly accept H+ than that of Acetic Acid (CH3COOH). This is because, the higher the pkb value of a compound the lower is the basicity pkb of H2O = 7 pkb of CH3COOH = 9.25
Strength of Acid
Strength of Acid depends on 1. Dissociation of an Acid into Proton (H+) 2. Environment / Solvent in which the acid dissociates This can be explained for both Strong and Weak Acid.
Table 3: Strength of Hydrochloric Acid in different Solvents
HCl
Hydrochloric Acid
H+
Proton
ClChloride ion
[Rapid Dissociation]
H2O
Water
H+
Proton
H3O+
Hydronium Ion
[Rapid Acceptance]
HCl
Hydrochloric Acid
H+
Proton
ClChloride ion
[Slow Dissociation]
CH3COOH
Acetic Acid
H+
Proton
CH3COOH2+
Onium ion
[Slow Acceptance]
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H2O and thus can rapidly accept H+ released by Acetic Acid. This is because; the higher the pkb value of a compound the lower is the basicity pkb of Ammonia = 4.75 pkb of H2O = 7
Acetic Acid in H2O acts as Weak Acid CH3COOH Acetic Acid H2O Water + H+ Proton H+ Proton + CH3COOAcetate Ion H3O+ Hydronium Ion [Slow Acceptance] [Slow Dissociation]
Acetic Acid in Liquid Ammonia acts as Strong Acid CH3COOH Acetic Acid NH3 Liquid Ammonia + H+ Proton H+ Proton + CH3COOAcetate ion NH4+ Ammonium ion [Rapid Acceptance] [Rapid Dissociation]
Protophillic Solvent
Protophillic Solvents are Proton loving Compounds for having high affinity to accept proton (H+) Basic in Nature; Also called Basic Solvents
Solvents used in Non Aqueous Acid Base Titration are 1. Protophillic Solvent 2. Protogenic Solvent 3. Amphiprotic Solvent 4. Aprotic Solvents
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Used to provide rapid dissolution of weak acids analytes where it can rapidly donate proton (H+) and behave like a strong acid Protophillic Solvents accept H+ released by the weak acid and form Solvated Proton Conjugate Acid of the Basic Solvent
React with the employed strong base titrant Conjugate Base of Weak Acid by reacting with Weak Acid Analyte Effect produced by these solvents is called Leveling Effect. E.g. Acetone, Ether such Dioxane, Liquid Ammonia
HWA
Weak Acid Analyte
H+
Proton
WAConjugate Base of WA
S
Protophillic Solvent
H+
Proton
SH+
Solvated Proton
SB
Strong Base Titrant
SH+
Solvated Proton
SBH+
Conjugated Acid of Strong Base
S
Protophillic Solvent
HWA
Weak Acid Analyte
SB
Strong Base Titrant
WAConjugate Base of WA
SBH+
Conjugated Acid of Strong Base
Protogenic Solvent
Protogenic Solvents are Proton generating Solvents for rapid release of proton (H+) Acidic in Nature; also called Acidic Solvents
Used to provide rapid dissolution of weak acid analyte where it can rapidly accept H+ and behave like a strong base. Protogenic Solvents generate / donate H+ and forms Conjugate Base of Acidic Solvent that rapidly accepts the H+ released by the Strong Acid titrant Effect produced by these solvents is called Leveling Effect. 8|Page
HS
Acidic Solvent
H+
Proton
B
Weak Base Analyte
H+
Proton
BH+
Conjugate Acid of Weak Base Analyte
HSA
Strong Acid Titrant
H+
Proton
H+
Proton
HS
Acidic Solvent
B
Weak Base Analyte
HSA
Strong Acid Titrant
BH+
Conjugate Acid of Weak Base Analyte
Amphiprotic Solvents
Amphiprotic Solvents are capable of acting as both H+ acceptor and donor.
Table 7: Acetic Acid Acting as a Protogenic Solvent
Solvents of this category produce Leveling Effect on both Weak Acid and Base Analyte E.g. Glacial Acetic Acid, Alcohols
CH3COOH
Acetic Acid
+ H+
H+
Proton
B
Weak Base Analyte
BH+
Conjugate Acid of Weak Base Analyte
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HA
Weak Acid Analyte
H+
Proton
H+
Proton
CH3COOH +
Acetic Acid
CH3COOH2+
Onium ion (Conj. Acid) Acidity of Compounds falls from strong to weak with increasing value from 1 to 14 on
Aprotic Solvents
Aprotic Solvents are chemically inert for neither accepting nor donating protons They are also called Neutral Solvents E.g. Hydrocarbons Carbon Tetrachloride (CCl4) Chloroform Benzene
the pka scale. And, Basicity of compounds falls from strong to weak with decreasing value from 14 to 1 on the pka scale. So, compounds which have pka value close to 1 (or 1 3) is a Strong Acid 1 (or 1 9) is Weak Base
Strong Acid
pka
Apomorphine 7.00
close to 14 (or 4 14) are Weak Acids 14 (or 9 14) are Strong Base
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Trimethylamine 9.74
So, Non aqueous acid base titration is performed for those compounds which are Partially soluble or insoluble in H2O Acidic compounds with pka 4 14 Basic Compounds with pka 1 4
Table 11: Titration of Weak Acid by Strong Base Titrant in a Basic Solvent
HWA
Weak Acid Analyte
H+
Proton
WAConjugate Base of WA
S
Protophillic Solvent
H+
Proton
SH+
Solvated Proton
SB
Strong Base Titrant
SH+
Solvated Proton
SBH+
Conjugated Acid of Strong Base
S
Protophillic Solvent
HWA
Weak Acid Analyte
SB
Strong Base Titrant
WAConjugate Base of WA
SBH+
Conjugated Acid of Strong Base
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layer of N2 (or other inert gases) is laid over the titrant. The entire device is sealed with Teflon stopcocks. Analytical / Titration Vessel for Analysis
The analyte reacts with the basic solvent to form the solvated
proton, a very reactive species and can also react with the atmospheric
Figure 4: Titration Vessel and Burette for Non aqueous Titration of Weak Acid
compounds So, A Three necked Flask is used to Protect the Analytical Solution from the atmosphere Obtain Accurate Result Perform the titration in
Controlled Environment The Middle neck of the flask provides the entry of burette tip. The Left and Right necks provide the entry and exit of the N2 gas (or other inert gas) respectively.
atmospheric Oxygen.
compounds
atmosphere by a special burette with reservoir which is flushed out with N2 (or other inert gases) and a
Practical Example
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A Practical Example of Non aqueous Titration of Weak Acid is the titration of Benzoic Acid in n butylamine by Sodium methoxide Here, Benzoic Acid (Weak Acid Analyte, pka = 4.2)
Sodium methoxide (CH3ONa, Strong Base Titrant) n butylamine (Basic / Protophillic Solvent) So, the reaction can be
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Here, the Protogenic Solvent acts as a base in the stronger acidic SA Titrant. When, the Analyte is dissolved in the Protogenic Solvent, they will react with each other to form 1. Conjugate (Conj.) Acid of WB 2. Conj. Base of SA Then, the Solvated Proton Species and Conjugate (Conj.) Base of Acidic
HSA
SA Titrant
+ + + +
HA
Acidic Solvent
H2A+
Solvated Proton Species
+ +
SAConj. Base of SA
WB
WB Analyte
HA
Acidic Solvent
HWB+
Conj. Acid of WB
H2A+
Solvated Proton Species
2HA
Acidic Solvent
WB
WB Analyte
HSA
SA Titrant
HWB+
Conj. Acid of WB
SAConj. Base of SA
Acidic Solvent
HSA
SA Titrant
+ + +
HA
Acidic Solvent
H2A+
Solvated Proton Species
+ + +
SAConj. Base of SA
WB
WB Analyte
H2A+
Solvated Proton Species
HWB+
Conj. Acid of WB
HA
Acidic Solvent
WB
WB Analyte
HSA
SA Titrant
HWB+
Conj. Acid of WB
SAConj. Base of SA
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Practical Example 1
Although Ephedrine is a Strong Base (pka = 9.6), it is titrated in non aqueous solvent for being poorly soluble in H2O.
Ephedrine in Glacial Acetic Acid is titrated by Perchloric Acid in Acetic Acid. The Reactions are illustrated as
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Practical Example 2
Ephedrine in Aprotic Solvents such as CCl4, Benzene, and CHCl3 etc. is titrated by Perchloric Acid in Dioxane.
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