Sep 042013
 


There are different theories which help to determine whether a substance is an acid or base. The major and generally accepted theories are given below:

1. Arrhenius Theory

According to Arrhenius theory, acid is a chemical substance which gives hydrogen ions only as cation when dissolved in water and base is a chemical substance which gives hydroxide ion only as anion when dissolved in water. Thus, HCl, HNO3, HClO3 are the examples of Arrhenius acid and NaOH, KOH are the examples of Arrhenius base.
Similarly, salt is a chemical substance which gives cation other than hydrogen ion and anion other than hydroxide ion when dissolved in water.
Acid and base react together to give salt and water as:

HCl + NaOH → NaCl + H2

Writing the above chemical equation in ionic form, we get,

H+ + Cl + Na+ + OH → Na+ + Cl + H2O

Eliminating the ions that appear in both sides, we get,

H+ + OH → H2O

Thus, acid base reaction may be defined as the reaction involving combination of H+ ion of acid with OH ion of base forming water molecule.

Limitations of Arrhenius Theory

  • Nature of H+ ion: Aqueous solution of acid does not contain H+ ion. The H+ ion produced by ionization of acid combines with water to form hydronium ion.

    H+ + H2 → H3O+

  • Limited scope: This theory can predict whether given substance is acidic or basic only when water is taken as solvent.
  • Some compounds like AlCl3, BF3, CO2 etc. do not contain hydrogen in their molecular formulae but they act as acid and some compounds like NH3 do not contain -OH in their molecular formulae but they act as base. This fact couldn’t be explained by this theory.
  • This theory couldn’t explain about the acidic properties of some cations like Ag+, Cu++ etc. and basic nature of some anions like O, Cl, Cl etc.

2. Lowry-Bronsted Theory of Acid and Base

According to this theory, acid is a chemical substance which can donate proton to base and base is a chemical substance which can accept proton from acid. Thus, acid is a proton donor and base is a proton acceptor.

For example,

HCl + NH3 ↔ NH4+ + Cl

In the above reaction, HCl donates a proton to NH3, thus HCl acts as acid and NH3 acts as base.

Similarly,

HCl + H2O ↔ H3O+ + Cl

Here, water gains a proton from HCl and hence acts as base.

H2O + NH3 → NH4+ + OH

In above reaction, water donates a proton to NH3 and hence acts as acid. Since water acts as both acid and base, it is called amphoteric substance. Again, let us consider a reaction,

acid-baseIn the given reaction, acetic acid donates a proton to water in forward reaction. Hence, CH3COOH acts as acid and H2O acts as base. Similarly, in backward reaction, CH3COO accepts a proton from H3O+. Thus, CH3COO acts as base and H3O+ acts as acid. Hence, CH3COOH and CH3COO are called conjugate acid-base pair.

Conjugate acid base pair is the pair of acid and base which can be obtained from each other by just loss or gain of a proton. Similarly, H2O and H3+ are other examples of conjugate acid base pair.

According to Lowry-Bronsted theory, acid-base reaction is the reaction involving formation of corresponding acid-base pair. Further, if an acid is strong, its conjugate base must be weak and vice-versa.

Limitations of Lowry-Bronsted Theory

Although this theory can predict acidic and basic character of many compounds, it still has some limitations. They are:

  • This theory could not explain about acidic nature of AlCl3, BF3 and CO2.
  • It could not explain about acidic nature of some metal ions like Ca++, Ag+ etc. and basic characters of some anions like O, Cl etc.

3. Lewis Theory of Acid and Base

Lewis theory of acid and base is based on negative charge and according to this theory, acid is a chemical substance which can accept lone pair of electrons and base is a chemical substance which can donate lone pair of electrons to acid. Thus, acid is acceptor of lone pair of electron and base is the donor of lone pair of electrons.

Let us consider a reaction,Ammonia and Hydrogen

In above reaction, lone pair of electrons are donated by ammonia by H+ ion. Thus, ammonia acts as Lewis base and H+ ion acts as Lewis acid.
Similarly,

BF3
In the above reaction, BF3 accepts a lone pair of electrons from ammonia and hence acts as acid.
According to Lewis theory, acid-base reaction is the reaction involving the formation of coordinate covalent bond between acid and base.

Limitations of Lewis Theory

According to Lewis theory, acid-base reaction is the reaction which involves the formation of coordinate covalent bond between acid and base. The formation of coordinate covalent bond is a slow reaction but acid-base reaction is fast reaction. Thus, this fact couldn’t be explained by Lewis theory.

Aug 082013
 

Indicators are the chemical substances which are used to determine the end points of titrations. Methyl orange, phenolphthalein, starch solution, erichrome black-T are some examples of indicators.

Indicators are used in acid-base titration and have different colours in acidic and basic mediums. For example, methyl orange has red colour in acidic medium and yellow colour in alkaline medium. Similarly, phenolphthalein has pink colour in alkaline medium and it has no colour in acidic medium.

Indicators used in acid-base titration are weak organic acids or bases. For example, methyl orange is a weak base and it exists in molecular form in alkaline medium and ionic form in acidic medium.

Indicators change their colour in certain pH ranges. The pH range of methyl orange and phenolphthalein are 3.1-4.4 and 8.2-10.0 respectively.

Choice of Indicator

Let us consider that a small amount of acid is taken into conical flask and alkali is added dropwise into it with the help of burette. On addition of each drop of alkali, it neutralizes H+ ion of solution resulting to the increase in pH of solution. The curve obtained by plotting pH of a solution against the volume of alkali added is called titration curve. At the neighbourhood of end point, addition of a drop of alkali neutralizes all acid solution and turns the solution into alkaline solution. Thus, there must be sudden increase of pH of solution near the end point. The shape of titration curve depends upon the nature of titration.

Titration Curves

As mentioned above, titration curve is the curve obtained by plotting pH of a solution against the volume of alkali added to it. On the basis of the acids and bases used in titration, the nature of titration curves can be categorized into four types. They are mentioned and explained below:

  1. Titration between strong acid and strong base (HCl versus NaOH): During the titration between strong acid and strong base, the sudden increase in pH of solution near end point ranges from 3 to 11. Thus, only indicators whose pH range lies in this pH interval can be used in such titration. Since pH ranges of both methyl orange (3.1-4.4) and phenolphthalein (8.2-10.0) lie above pH interval, both of them can be used in such titration.Titration_1
  2. Titration between strong acid and weak base (HCl versus NH4OH): In titration between strong acid and weak base, the sharp increase in pH ranges between 3 to 8. Since the pH range of methyl orange lies above the pH interval, only methyl orange can be used as indicator in such titration.Titration_2
  3. Titration between weak acid and strong base (CH3COOH versus NaOH): In titration between weak acid and strong base, the sudden increase of pH near end point ranges between 6 to 11. The pH range of only phenolphthalein lies above pH interval. Hence, only phenolphthalein can be used as indicator in such titration.Titration_3
  4. Titration between weak acid and weak base: In titration between weak acid and weak base, the sudden increase in pH ranges between 6 to 8. Since no any indicator can change its colour in such a small pH interval, the titration between weak acid and weak base cannot be carried out by using indicators.Titration_4