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Chemical Equilibrium And Acids - Bases

     Compounds are broadly classified into acids, bases and salts. Many inorganic, biochemical reactions involve acids and bases. Many theories came to explain acids & bases. According to Arrhenius theory, acids give H+ ions, bases give OH- ions in their aqueous solutions. But this theory was failed to explain acidic behaviour of solutions
of CO2, SO3 and basic nature of solutions of NH3, Na2O etc. 
       Lowry - Bronstead introduced a new theory i.e. proton theory. According to them
Acid: A Substance that donates proton to another substance e.g. HCl, HNO3.
Base: A Substance that accepts proton from another substance.
                             e.g.: NH3, Cl-, HSO4 -
Conjugate acid - base pair: The acid-base pair which differs by a proton.
                             NH3 + H2 NH4+ + OH-
                            H2O & OH-; NH4+ & NH3 are conjugate acid-base pairs.


Neutralisation: The transfer of a proton from acid to base.
e.g.: One proton of H2O is transferred to NH3 to form NH4+
         A strong acid has a weak conjugate base and a strong base has a weak conjugate acid some compounds like H2O, NH3, ions like HCO3-, HSO4- can act as both acid or base, called amphiprotic.
        Acceptance or donation of protons takes place only in the presence of other substance.
This theory does not explain the behaviour of compounds like BF3, BCl3, AlCl3. Water is levelling solvent. Water equalises H3O+ concentration for acids, OH- concentration for bases, is called 'levelling effect'. So relative strengths of acids or bases are studied in solvents like NH3 or CH3COOH. The order of strength of common acids in acetic acid is:
                           HClO4 > HI > HBr > H2SO4 > HCl > HNO3 > H3PO4 > H2CO3.   
  Acidic, basic behaviour is well explained by Lewis interms of electrons by his "Lewis theory".

According to Lewis theory
Acid: Any substance that accepts electron pair to form a coordinate covalent bond.
                                             eg: BF3, BCl3
Types of Lewis acids:
¤ All cations : CO+3, Fe+3
¤ Elements with electron sextet: O, S
¤ Molecules with multiple bonds: CO2, SO2
¤ Molecules with available d-orbitals: SF4, SiF4
¤ Molecules with incomplete octet: AlCl3, BF3
Base: Any substance that donates electron pair to form a coordinate covalent bond
                                               eg: H2O, NH3.
Types of Lewis bases:
¤ All anions: F-, Cl-
¤ Molecules with lone pairs: ROH, NH3
¤ Molecules with multiple bonds: C2H2, C2H4
 All bronstead bases are also Lewis bases. For example NH3 accepts a proton to form NH4+ So it is bronstead base, NH3 donate one electron pair so it is Lewis base. But all Lewis acids need not be Bronstead acids as they need not contain protons (eg: Fe+3, Cu+2, SO2)
    Lewis theory does not explain the strength of acids and bases. Reaction between HCl, H2SO4 and NaOH, KOH do not form any dative bond and the reaction is fast.
                       HClO4 , H2SO4, HNO3, HCl are strong acids.
    CH3COOH, H2CO3 are weak acids. KOH, NaOH, CsOH are strong bases. NH4OH, Cu(OH)2 are weak bases. The strength of an acid or base can be known from their degree of ionization
(α = alpha). For strong acids or bases it is equal to 1. For weak acids or weak bases it is lessthan 1.


Ionization constant of weak acid (Ka)
      Let us suppose a weak acid HX is partially ionised in aqueous solution:
                             HX (aq.)  +  H2O (l)     H3O+(aq.)    +    X- (aq.)
Initial concn.                 C                                    O                          O
Equilibrium concn.     c - cα                              cα                         cα

K [H2O]2  =  Kw = [H+] [OH-]
       The product of the concentration of H+ and OH- ions in water or in aqueous solutions is known as ionic product of water. At 25°C, Kw is 1.0 × 10-14 moles2/lit2. Kw increases with the increase in temperature.


Significance of Kw:
¤ If [H+] or [OH-] is known the other can be calculated from Kw
¤ For a neutral liquid, [H+] = [OH-] =

 = 1.0 × 10-7 moles/lit
¤ For acidic solutions [H+] > 10-7 ( ... [H+] > [OH-])
¤ For basic solutions [H+] < 10-7 [... [H+] < [OH-])
Dissociation constant of water (K):
               [H2O]  H+  +  OH- at 298 K
         
Concept of pH
¤ pH concept was introduced by S.P.L. Sorenson to express the acidity of a dilute solution accurately. "negative value of logarithm(to the base 10) of [H+] ion concentration (moles/lit) in a solution is known as pH".
              pH = -log10 [H+]
              pOH = -log10 [OH-]            (Hint: p = -log 10)
              pH + pOH = 14 (at 298 K)
       Solutions can have pH from 0 to 14. Acidic solutions have pH from 0 to 7, that of basic solutions have 7 to 14 for neutral solutions pH = 7. pH = 0 means solution is strongly acidic
(e.g.: 1 N HCl). For more concentrated acidic solutions pH can be negative, for more concentrated basic solutions pH can be more than 14. If the pH of a solution remains constant, it is called buffer solution.


Buffer solution: The solution whose pH remains constant upon the addition of few ml of strong acid or strong base.
Acid buffer solution: The solution which is formed by mixing weak acid and its salt with a strong base
                           e.g.: CH3COOH  +  CH3COONa
Base buffer solution: The solution which is formed by mixing weak base and its salt with a strong acid.
                            e.g.: NH4OH  +  NH4Cl
Working of acid buffer: When few ml of strong acid is added to acid buffer
     (eg.: CH3COOH + CH3COONa), H+ ions of added acid react with CH3COO- ions to form a weak acid.
                          CH3COO- + H+ CH3COOH


      As there is no change in H+ concentration, pH of the buffer remains same. When few ml of strong base is added to the buffer, OH- ions react with H+ ions of acid buffer to form H2O.
                 CH3 COOH + OH- CH3COO- + H2O
      As there is no change in OH- concentration, pH of the buffer remains same.
Working of base buffer: When few ml of strong acid is added to base buffer.
                      (e.g.: NH4OH + NH4Cl), H+ ions of added acid reacts with OH- ions of base to form weak ionised water. As there is no change in H+ ion concentration, pH of the buffer remains same.
                       NH4OH + H+ NH4+ + H2O

Buffer capacity of a buffer is maximum when pH = pKa or pOH = pKb [[salt] = [Acid] or [base]]                
A buffer solution shows its effective action only in the range of pH = pKa ± 1
(e.g.: CH3COOH + CH3 COO Na has pKa = 4.76. So it works well from pH 3.76 to 5.76). A buffer with greater  value is a good buffer.


Applications of buffer solutions:
¤ Buffers are used in softening of hard water.
¤ Buffers play an important role in biochemical reactions. Blood is a buffer
          (H2CO3 + NaHCO3) with pH of 7.4
¤ Buffers are widely used in enzyme catalysed reactions, Chemical analysis and industrial synthetic processes.
Hydrolysis of Salts:
        When acid reacts with base, a salt is formed. When a salt is added to water, it gets hydrolysed. "Anion or Cation or both of a salt react with water to give OH- ions or H+ ions or both is known as salt hydrolysis".
Hydrolysis of NH4Cl:
      NH4Cl salt is formed from a weak base NH4OH and a strong acid HCl. So NH4+ (conjugate ion) is strong acid, which undergoes cationic hydrolysis to give H+ ions.
         Nature of NH4Cl solution is acidic. pH < 7
     Hydrolysis Constant (Kh) for NH4Cl salt Kh=  
          pH = 7 -   [pKb + log c]
Hydrolysis of CH3COONa: CH3COONa Salt is formed from a weak acid CH3COOH and a strong base NaOH. So CH3COO- is strong base, which undergoes anionic hydrolysis to give OH- ions. Nature of CH3COONa solution is alkaline. pH > 7.
                           Kh =   
                  pH = 7 +  

[pKa + log c]
Hydrolysis of CH3COO NH4: CH3COONH4 Salt is formed from a weak acid CH3COOH and a weak base NH4OH. It involves both anionic as well as cationic hydrolysis. The nature of the solution may be neutral or acidic or basic depending upon the relative degrees of ionization of the weak acid and weak base.
                                      
                     pH = 7 +  [pKa - pKb]        or       pH =  [pKw + pKa - pKb]


Hydrolysis of NaCl: NaCl is formed from strong base NaOH and strong acid HCl. So Na+ is weak acid and Cl- is weak base both involves no hydrolysis. Nature of the solution is neutral and its pH = 7.
¤ Common ion effect and solubility product are very important Phenomena in analytical chemistry, purification of salts, and in gravimetric analysis etc.
Common ion Effect: The suppression of ionization of a weak electrolyte, when a solution (having common ion with weak electrolyte) of strong electrolyte is added to the solution of weak electrolyte.
pplications of Common ion effect:
¤ In precipitation purification of NaCl by passing HCl gas
¤ In controlling H+ ion concentration in buffer solution
¤ In Analytical Chemistry
¤ Precipitation of cations of groups in qualitative analysis.
¤ In grallimetric analysis.


Solubility: The amount of solute which can be dissolved by 100 grams of a Solvent at a given temperature. A Solute dissolves in a Solvent when hydration energy is greater than lattice energy. The solubility increases with increase of temperature, when the heat of solution is endothermic.
Solubility Product: The product of molar concentrations of cations and anions of salt
present in a saturated solution. Solubility product of a Salt Ax By can be explained as follows.
                                 AxBy  xA+ + yB-
     Solubility Product (KSP) = [Ay+]x [Bx- ]y


Applications of Solubility Product:
¤ In the precipitation of III group hydroxides, sulphides of II and IV group cations.
¤ In the manufacture of sodium bicarbonate.
solubility product helps in predicting precipitation on mixing two solutions. If the ionic product is greater than solubility product, precipitation takes place, If it is less than that of KSP, no precipitate is formed. If ionic product is exactly equal to KSP, precipitation just starts.

Posted Date : 04-08-2021

గమనిక : ప్రతిభ.ఈనాడు.నెట్‌లో కనిపించే వ్యాపార ప్రకటనలు వివిధ దేశాల్లోని వ్యాపారులు, సంస్థల నుంచి వస్తాయి. మరి కొన్ని ప్రకటనలు పాఠకుల అభిరుచి మేరకు కృత్రిమ మేధస్సు సాంకేతికత సాయంతో ప్రదర్శితమవుతుంటాయి. ఆ ప్రకటనల్లోని ఉత్పత్తులను లేదా సేవలను పాఠకులు స్వయంగా విచారించుకొని, జాగ్రత్తగా పరిశీలించి కొనుక్కోవాలి లేదా వినియోగించుకోవాలి. వాటి నాణ్యత లేదా లోపాలతో ఈనాడు యాజమాన్యానికి ఎలాంటి సంబంధం లేదు. ఈ విషయంలో ఉత్తర ప్రత్యుత్తరాలకు, ఈ-మెయిల్స్ కి, ఇంకా ఇతర రూపాల్లో సమాచార మార్పిడికి తావు లేదు. ఫిర్యాదులు స్వీకరించడం కుదరదు. పాఠకులు గమనించి, సహకరించాలని మనవి.

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