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Tuesday, October 23, 2018

BRONSTED LOWERY ACID-BASE CONCEPT

According to Bronsted theory the species which donate protons (H+) in any medium is consider as acid and the species which accept proton is consider as base.
Acid and base characters are realised in the presence of each other.
For example
CONJUGATE ACID-BASE PAIRS
(1) conjugate pair is acid-base pair differing in single proton (H+)
(2) conjugate acid is written by adding  H+ and conjugate is written by removing H+
.
(3) Strong acid has weak conjugate base and vice versa. Similarly strong base has weak conjugate and vice versa.

(4) Equilibrium always moves from strong acid to weak acid and strong base to weak base.


(5) Conjugate acid - base pair differ by only one proton. Reaction will always proceed from strong acid to weak acid or from strong base to weak base.
MERITES OF BRONSTED CONCEPT:
(1) the role of solvent clearly defined.
(2) the acidic and basic  character may be observed in non aqueous medium also .
(3) the acidic ,basic or Amphoteric nature of most of the substance may be defined.
(4) the acid having greater tendency to donate protons are stronger acid and base  having greater tendency to accept protons are stronger base .
(5)In conjugate pair ,if one is strong then other must be weak .
The weak acid or base are normally determined by comparing the the stability of different acid or base
DEMERITES OF BRONSTED CONCEPT:
(1) Proton is a nuclear particle hence reaction should not explained in term of proton.
(2) the neutralized process becomes multiples step process.
(3) Most of the Amphoteric solvent become Amphoteric.


AMPHOTERIC SPECIES (Amphiprotic):
The species which have a tendency to donate proton as well as accept proton (H+) such species are known as Amphoteric species.
For example H2
O,NH3 HS- ,HPO3- ,HC2OO4- , H2O4 etc

ILLUSTRATIVE EXAMPLES:
(1)The conjugate base of HCO3 is –
  (A) H2CO3        (B) CO2             (C) H2O      (D) CO3 
(2) The conjugate acid of HSO3- is -
  (A) SO32-          (B) SO42-                  (C) H2SO4    (D) H2SO3

(Ans: 1-D 2-D)
                                                                 @@@

ARRHENIUS ACID-BASE CONCEPT

CHARACTERS OF ACIDS:
(1) acids convert blue litmus to red and methyl orange  indicator to  red .
(2) Sour in taste.
(3) It liberate hydrogen gas with active metals.
(4) Acids neutralised the effect of base 
(5) acids increases the conduction of water.
CHARACTERS OF BASES:
(1) bases convert the red litmus to blue and methyl orange indicator to yellow.
(2) Phenylphthlene indicator (white) to pink.
(3) Bitter in taste and soapy in touch.
(4) Bases neutralised the effect of acid.
(5) They increases conductance of water.
ACID BASE CONCEPT:
(1) ARRHENIUS ACID-BASE CONCEPT
(2) BRONSTED LOWERY ACID-BASE CONCEPT 

(3) LEWIS ACID-BASE CONCEPT

(1) ARRHENIUS ACID-BASE CONCEPT
the substance which produces H+ in aqueous solution is consider as acid and the substance which give produces OH- in aqueous solution is consider as base
Arrhenius theory depend upon dissociation of water.







Type of Arrhenius acids:

Type of Arrhenius Bases :
         

Feature of Arrhenius theory:

(1) OH¯ ion is present also in hydrated form of H3O2¯, H7O4¯, H5O3¯
      H+ ion is present also in hydrated form of H3O+, H5O2+, H7O3+, H9O4+
(2) Neutralisation reaction can be easily explain by the Arrhenius theory .acids furnishing H+ ion  in water to large extent are strong acid.

Strength of acid or base:

(3) If Ka increases then concentration of H+ increases hence acidic strength is increases.
Similarly the base furnishing OH- ions to the large extent are strong base
Kb is dissociation constant for bases, if Kb is increases OH- increases, hence basic strength of base

(4)The term strong is used only for those acids or bases or bases which dissolved almost completely in water.

LIMITATIONS OF ARRHENIUS THEORY
(1) This theory explain nature of a substance only aqueous medium . It cannot be applied for non aqueous solution.
(2) It could not explain formation of hydronium ions like H3O- , H5O2- , and H7O3- .
(3) the nature of aqueous solution of AlCl3, CuSO4 ,BF3, B(OH)3 etc are acidic and aqueous solution of NH3 ,NaCO3 ,RNH2 R2NH,  R3N , C2H5N  etc are basic in nature cannot be explain by Arrhenius Concept.
(4) there are many  Amphoteric hydroxide Zn(OH)2  Al(OH)3 ,Pb(OH)2 , which cannot be  explain  by Arrhenius Concept.
(5) Arrhenius explain only when H+ is released it cannot explain when H+ is taken.
                                                 

Sunday, October 21, 2018

SPONTANEOUS AND NON SPONTANEOUS PROCESS

SPONTANEOUS PROCESS: Those process which have natural tendency to take place ,they may or may not require initiation.
For example
(1) Flow of water from higher level to lower level .
(2) Flow of heat from high temperature to lower temperature.
(3) Radioactivity
(4) Cooling of cup of tea .
(5) Evaporation
(6) Condensation 
(7) Sublimation
(8) Burning of candle
(9) Dissolution of salt and sugar in water
(10) Burning of fuel
(11) melting of ice at room temperature.
NON SPONTANEOUS PROCESS: All spontaneous processes are non spontaneous processes in reverse direction it requires spot of external energy for their progress.
CRITERIA FOR SPONTANEITY:
(1) If dS universe is greater than Zero  then process is spontaneous (reversible)
(2) If dS is Zero then process is in reversible state of equilibrium
(3) If dS is lower than Zero then  process is non spontaneous
For  a spontaneous process entropy of univers is greater than Zero . In order to use entropy has a sole criteria , we need to have information about system as well as surrounding.
dS(system) + dS(surr) is greater than  Zero
.
.
.
.
In order to explain the spontaneous behaviour by using the parameters of system we can established  two criteria.
(1) Randomness
(2) Criteria of energy
A spontaneous process is one in which energy ( enthalpy) decreasing and Randomness of system increasing.
For spontaneous proceDH=-ve and dS=+ve

Saturday, October 20, 2018

LEWIS ACID-BASE CONCEPT:

According to Lewis acid base theory- acids are electron pair accepter (electron deficient) and bases are electron pair donor and the combination of Lewis acid and Lewis base occur through coordinate bond formation.
For example

Others examples of Lewis acid-base neutralization.

Lewis acids:

(1) Cations are act as Lewis acids example, H+ , Ag+ , Cu+2 , Na+ , Fe+2 , Hg+2  etc.
(2) Electron deficient compounds are act as Lewis acids for examples BF3 ,ACl3 ,BCl3 ,FeCl3 etc 
(3)
The compounds  which central atom with available vacant d-orbital  can add additional pairs of electrons even though it already has an octet or more of electrons act as Lewis acids for examples SiCl4,PCl5, SOF4, SbCl3, SbF5 ,SnCl4, IF7, SF4 etc 

(4) Compounds containing multiple bonds for example CO2 , SO2, SO3 ,CS2 etc.

Lewis bases:

(1) Anions are act as Lewis base H- ,CH3- ,NH2- , OH- , X- etc. but all the anions are not Lewis base for example (PCl5)
(2) The Neutral molecules having lone pairs of electrons act as Lewis base for examples NH3 ,R-NH2, R-NH-R, R3-N, H2O , R-OH ,R-O-R , PH3, R-PH2 , R2PH ,R3P , H2S , R-SH , R-S-R etc
(3) Compounds with non polar multiples bond  are also act as Lewis base, example Alkenes(C2H4) , Alkynes(C2H2 ) Dienes, polyenes, benzene, Polynuclear homoaromatic compounds. (Ligand in coordination compounds)

Chemical Reactions according Lewis acid-base concept:

We can now write equations for many reactions that involve a Lewis acid reacting with a Lewis base. The following are a few examples:


Acid-base behavior according to the Lewis theory has many of the same aspects as does acid-base theory according to the Brønsted–Lowry theory.

(1)There is no acid without a base. An electron pair must be donated to one species (the acid) by another (the base).

(2) An acid (or base) reacts to displace a weaker acid (or base) from a compound.

(3)The interaction of a Lewis acid with a Lewis base is a type of neutralization reaction because the acidic and basic characters of the reactants are removed.

An acid-base reaction takes place readily between BF3 and NH3 ,

                                         BF3  +NH3 → H3N:BF3

However, when the product of this reaction is brought into contact with BCl3, a reaction takes place:

                                  H3N:BF3 +BCl3 → H3N:BCl3  + BF3

In this reaction, a Lewis acid, BF3 , has been replaced by essentially a stronger one BCl3 .  And replacement of Lewis  acid by other Lewis acid follow Second order Nucleophilic substitution (SN2).

Merits of Lewis concept:
(1)
The acid/base nature of substance may also defined without any solvent.
(2) It is highly useful to explain coordination compounds in which central metal atom into behave as Lewis acid and ligands behave as Lewis base.
(3) The acid having greater tendency to accept lone pair bare stronger acid and base have greater tendency to donate lone pair are stronger base.

Demerites of Lewis concept: 
(1) It is extremely generalized Concept , almost all the compounds either become acid or base  by this Concept.


Related Questions:

Thursday, October 18, 2018

Levelling effect and relative strength of acids:

When strong acids like HClO4, HCl, HBr, HI, HNO3 etc are dissolved in water they are equally ionised (100%) it means they are equally strong in water this is called levelling effect of water.
Similarly for strong bases also , NaOH, KOH  Ca(OH)2 etc are in water behave the same. hence relative strength of strong acids or base can not be compare in water .
(1) Water does no show levelling effect for weak acids or base because they are ionised upto different extent in water.
(2) All the acids are stronger than H3O+ ion, consider as strong acids and weak than H3O+ ion are consider as weak acids.
(3) All the bases stronger than OH- are consider as strong base and weaker than OH-, then they are consider  as weak base.

Definition: If more than one acids or bases are showing same acidic or basic strength in same solvent it is called labelling effect and the solvent is called labelling solvent for example:

(1) HClO4 and HI equally dessociation in aqueous medium (99.99%)  it means they have equal strength.

(2) HCl, HNO3  and H2SO4 are equally strong in water because their strength are “levelled” to solvent species H3O+. only by putting them into a more acidic solvent do they weak acids. With determinate Pka values which differetiate their strengths. Thus in glacial ethanoic acid (acetic acid ) as solvent, the order of  acidic strength is as: H2SO4 > HCl > HNO3 .

(3) Similarly HF and HCl are equally dessociation in NaOH (100 %).
If their strength differ in same solvent ,it is called 
differential effect and the solvent is called differential solvent.

(4) For example HClO4 dessociate 99.99 % in acetic acid while HI dissociate 99.8% in acetic acid, it means acidic strength of HClO4 is more than HI in acetic acid.

(5) Many of inorganic oxoacid are strong acid (with more negative Pka value) inaqueous solution. But, as we have seen, use of solvent with a lower proton affinity than water like acetic acid, makes it possible to differentiate between the strength of these acids and measure Pka value.

H2CO3 < H3PO4 < H2SO4 < HClO4 (Increasing acidic sterngth) these acidic strength can  also explain if the folmulae of the these oxy acids are written as base or OH formate or like that OC(OH)2 < OP(OH)3< O2S(OH)2< O3Cl(OH) then it is clear that the acidic strength incrases as the number of oxygen atoms not involve in O-H bonding increases.

The reason behind levelling and diffential  effect is ability of solvent to donate or accept protons .
For acids, acidic solvents are differential and basic solvent are levelling.

Related Questions:

What are "pyro" oxy acids?

What are "Ortho" or "Meta" oxyacids?

What is Meta Boric Acids?

What are the structural difference between oxides ( P4O6 and P4O10) of phosphorous?

What are common structural features of oxides (P4O6 and P4O5) of phosphorous?

What is "calgon" ? Give structure and its uses?

Structure of Oxy acids of Phosphorous:

What is structure of (HPO3) metaphosphoric acid?

What is metaphophoric (HPO3)?