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.

                                                 

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

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^- ,NH^2- , 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 (S_N²).

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:

Why is BCl3 a strongerLewis acid than BF3 ?

Arrange the silicon halides into decreasing order of Lewis acids Character? SiF3, SiCl3, SiBr3, SiI3

Silianol (SiH3OH) is more acidic than methanol (CH3OH) why?

Why thionyl chloride behaves as Lewis acid as well as Lewis base?.

What is Lewis acid character order of Boron halides, arrange in increasing order?

What are the order of extent back bonding, Lewis acid character and nucleophilicity of (BF3, BCl3, BBr3, BI3)boron trihalides?

Arrange the silicon halides into decreasing order of Lewis acids Character? SiF4, SiCl4, SiBr4, SiI4

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)?

VOLUME STRENGTH OF H2O2(aq)

 Hydrogen peroxide is a colourless liquid used as bleaching agent in some food and act as oxidising as well as reducing agent.The most common use of hydrogen peroxide is in cosmetic including personal care, hair dye, bleach shampoos conditioners and first aid  antiseptic.
Hydrogen peroxide also used as propellant for torpedoes on account of its exothermic decomposition.

The strength of Hydrogen peroxide expressed several ways like Volume strength, W/V % (% strength), Molarity, Normality etc.

COMMERCIAL LABELLING OF H₂O₂ AS ‘X’ VOLUME :  

Commercially H₂O₂ labelled as 'X' volume H₂O₂ (at P=1 ATM and T=273 K)
Where 'X' may be  10V, 20V, 30V, 40 V etc. 

Here  'X' Volume H₂O₂ means that 1ml of such solution of hydrogen peroxide on decomposition  produce 'X' ml of oxygen (at P=1 ATM and T=273 K).

For example 10 Volume H₂O₂ means that 1ml of such solution of hydrogen peroxide on decomposition  produce '10' ml of oxygen (at P=1 ATM and T=273 K).

W/V % or PERCENTAGE STRENGTH OF  H₂O₂SOLUTION: 

The amount of H₂O₂ in gram present in 100 ml of aqueous solution of H₂O₂. Called (w/v) or percentage strength.

Illustration:  taken 10 V (Vol) H₂O₂:

By Stoichiometric calculations:

Thus 1ml, 10 V labelled H₂O₂ (aq) solution contains 0.0303 gm H₂O₂.

Similarly 100 ml, 10 V labelled H₂O₂ (aq) solution contains 0.0303x100=3.03 gm of H₂O₂. This called W/V % or percentage strength of H₂O₂ solution.

MOLARITY AND NORMALITY OF H₂O:

 And 1000 ml, 10 V labelled H₂O₂ (aq) solution contains 0.0303x1000=30.30 gm H₂O₂. It means 30.30 gm H₂O₂ dissolved in 1000 ml (1L) Solution.

  Hence Molarity of 10 V H₂O₂ Solution is = 0.89 M

  Normality of 10V H₂O₂ (aq) Solution: 

Hence Normality of 10 V H₂O₂ Solution is =1.79 N

 We also know that NORMALITY= MOLARITY X n-FACTOR

                              Normality= O.89x2 =1.79 N

ALTERNATIVE MATHAD TO DTERMINED MOLARITY AND NORMALITY:

Volume of O₂ provided by 1unit Volume of H₂O₂ aq Solution

ILLUSTRATIVE EXAMPLES:

EXAMPLE: (1) A solution of H₂O₂ has Normality N/1.7 calculate w/V strength of this solution?.
EXAMPLE: (2) Convert 20 V H₂O₂ into % strength or w/v strength?
EXAMPLE: (3) Convert 6.8 % strength of H2O2 into Volume strength?
EXAMPLE: (4) 500 ml of a H₂O₂ solution on decomposition produce 2 mole of H₂O. Calculate the Volume strength of of H₂O₂ of solution? (Given Volume of O2 measured at 1atm and 273 K)  (Ans - 44.8 V)
EXAMPLE: (5) What is the percentage strength of "15" volume of H₂O₂?
EXAMPLE: (6) What volume of H₂O₂ solution of "11.2 volume strength is required to liberate 2240 ml of O₂ at NTP?
EXAMPLE: (7) 30 gm Ba(MnO₄)₂ sample containing inert impurity completely reacting  with 100 ml "28" volume strength of H₂O₂ in acidic medium then what will be the percentage purity of Ba(MnO₄)₂ in the sample ?. (Ba=137, Mn = 55, O =16)
EXAMPLE: (8) the strength of "20 Volume" H₂O₂ is equal? 
EXAMPLE: (9) What is weight of available oxygen from a solution of H2O2, if 20 ml of this solution need 25 ml, N/20 KMnO4 for complete oxidation? (Ans- 0.25)
EXAMPLE :( 10) calculate molarity of 44.8 V strength of H₂O₂ aq Solution?.

EXAMPLE: (11) calculate the molarity of H₂O₂ if 11.2 ml H₂O₂ require 30 ml of 0.5 M K2Cr2O7 for its complete oxidation; also calculate the Volume strength of H₂O₂? (Ans M=45/11.2 and volume strength=45)