Ionic Equilibrium

Ionic Equilibrium
Arrhenius Concept CA xx
+
 An acid is a substance which can furnish H ion CA H O+
in aqueous medium. 3
 E.g. HNO3 (aq)  H+ (aq) + NO3– (aq) CB
 A base is substance which can furnish hydroxyl H2O
ion (OH–) in aqueous medium. H2O
 E.g. NaOH (aq)  Na+ (aq) + OH– (aq) CA H O
2
CB CA OH-
OH-
Bronsted Lowry Concept CB
O2-
 Acid = donate proton CB
 Base = accept proton xx
 E.g. HCl + H2O  H3O+ + Cl–
Acid Base
CA xx
Conjugated Acid Base Pair CA NH +
4
 Acid becomes base after losing proton while CB
base become acid after accepting proton. NH3
 E.g. HCl + H2O  H3O+ + Cl– NH3
Acid1 Base2 Acid2 Base1 CA
NH3
 Conjugate base of an acid formed by loss of CB
NH2 - CA NH -
proton. 2
 Conjugate acid of a base formed by gain of CB CA NH2-
proton NH2-
CB N3-
CA H CO CA HCN
2 3
CB
- -
xx
HCO3 CN
CB CB N.B.
CO32- xx
O O O
|| || ||
CA H PO CA H PO P P P
3 4 3 3

H2PO4- H2PO3- OH OH OH OH OH H OH H H
CB CB basicity = 3 basicity = 2 basicity = 1
HPO42- HPO32-
 H2O is amphoteric i.e. can act as acid as well as
CA CA base.
H2PO3- H3PO2  H2CO3 + H2O  H3O+ + HCO3–
Acid1 Base2 Acid2 Base1
HPO32- H2PO2-
 HCO3 + H2O  H2CO3 + OH–
–
CB CB Base1 Acid2 Acid1 Base2
xx xx
 Conjugate base of a strong acid is a weak base.
 Conjugate base of a weak acid is a strong base.
 Conjugate acid of a strong base is a weak acid.
 Conjugate acid of a weak base is a strong acid.

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 Ionic Equilibrium
 In presence of strong acid, another acid behaves B(OR)3 is weaker lewis acid than BR3 due to
as base. resonance stabilisation of the former.
 E.g. HClO4 + H2SO4  H3SO4+ + ClO4– BF3 < BCl3 < BBr3 < BI3
Acid Base
BF3 involves stronger 2pπ−2pπ back bonding
between lone pair orbital of Fluorine atom & vacant
Lewis Concept 2p orbital of B atom. The extent of back bonding
decreases inBCl3 (2pπ−3pπ) to BBr3 (2pπ−4pπ). BI3
 Acid – accept lone pair of electron has almost no back-bonding.
 Base – donates lone pair of electron.
 Example of lewis acid –  Acidic strength α Charge density of central atom
(i) Molecules having incomplete octet – BF3, AlCl3, ( )
BeCl2, etc. Alkali metal ions show essentially “no” acidity.
(ii) Cations – Al3+, Cu2+, Fe2+, etc. Alkaline earth metal ions are only slightly acidic.
(iii) Metals in complex compound – Ni in Ni(CO)4. +2 transition metal ions are weakly acidic.
(iv) Molecules in which central atom has vacant d- +3 transition metals are moderately acidic.
orbitals – SiX4, SnX4, GeX4, TiCl4, SF4, SeF4, etc. Metal ion Ka Metal ion Ka
 Example of lewis base – Fe3+ 6.7 x 10–3 Fe2+ 5 x 10–9
–4
(i) Molecules having one or more unshared pairs of Cr 3+
1.6 x 10 Cu 2+
5 x 10–9
–5
Al3+
1.1 x 10 Ni2+
5 x 10–10
electron – NH3, H2O, ROH, etc. –5
Sc 3+
1.1 x 10 Zn 2+
2.5 x 10–10
(ii) Anion – Cl–, OH– etc.
(iii) Ligands in complex compounds – CO in Fe3+ > Fe2+
Ni(CO)4. Sn4+ > Sn2+
(iv) Carbon – carbon multiple bond – C=C & CC. SbX5 > SbX3
[Fe(H2O)6]3+ > [V(H2O)6]3+ > [Cr(H2O)6]3+ >
[Sc(H2O)6]3+ > [Al(H2O)6]3+ > [La(H2O)6]3+
Factors Affecting Strength of [Be(H2O)n]2+ > [Cu(H2O)n]2+ > [Mg(H2O)n]2+ >
[Ca(H2O)n]2+ > [Ba(H2O)n]2+
Lewis Acid .
N.B.
 An atom that can accept only one lone pair General order of Lewis acidity: BX3 > AlX3 > FeX3 >
(e.g.,B) is more acidic than an atom that can accept GaX3 > SbX5 > InX3 > SnX4 > AsX5 > ZnX2
more than one lone pair of electrons (e.g., Fe or Sn).
 Acidic strength  (if central
Factors affecting acidic strength
atom belongs to same group)
BX3 > AlX3 > GaX3 >InX3 Acidic strength  EN of NM
BR3 > AlR3 (for hydracid and oxyacid)
PCl3 > AsCl3 > SbCl3.  Size of NM (for hydracids)
CuX2 > AgX2 > AuX2
 ON of NM
PX5 > AsX5 > SbX5
ZnX2 > CdX2 > HgX2 (for oxyacid/oxides of non-metal)
ScX3 > YX3 > LaX3  S-character of NM
CuBr2 > CdBr2  ewg (–I, –M, –HC)

 Acidic strength  EN/–IE of surrounding atom
Me3B < BH3 < BF3  Ka
AlF3 > AlCl3 > AlBr3 > AlI3 

 Acidic strength   Stability of CB

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 Ionic Equilibrium
N.B.
 General Acidic Strength
Types of Solvent
HSbF6 (super acid) > HClO4 > HI > HBr  H2SO4 >  Protophilic solvent – accepts H+, e.g., H2O,
HCl > HNO3 > H3O+ > H3PO4 > HF > HNO2 > ROH, liquid NH3.
RSO3H > CH3COOH > H2CO3 > H2S > HCN >  Protogenic solvent – produces H+, e.g., H2O,
C6H5OH > CH3OH >H2O > ROH > C2H2> NH3 > HCl, CH3COOH.
C2H4 > C2H6  Amphiprotic solvent – donate as well as accept
H+, e.g., H2O.
 Protonated aldehyde/ketone/ester/carboxylic
 Aprotic solvent – neither accepts nor donates
acid/phenol > –SO3H > protonated alcohol/ether > –
H+, e.g., alkanes, aromatic hydrocarbon, CCl4, CS2,
COOH
CH2Cl2, acetone, DMSO, DMF, acetonitrile .
 EN of sp C > EN of sp3 N
 EN of O+ (sp3) > N+ (sp3) > O (sp3) > N sp3
Effect of Solvent
Factors Affecting Acidic  Strength of acid also depends on capability of
solvent to accept proton.
Strength of Hydracid (HA)  H2O has greater tendency to accept proton and
all strong acid appears almost equally strong in H2O.
 Strength  E.N. of A (non metal)
This phenomenon is called “Levelling effect”.
Example:
 Strong acid as well as weak acid appears equally
 CH4 < NH3 < H2O < HF strong in liquid ammonia because NH3 has very high
 SiH4 < PH3 < H2S < HCl tendency to accept proton.
(In PT, strength of hydracids  L2R)
 Strength  size of A.
Example: Degree of Dissociation ()
 NH3 < PH3 < AsH3 < SbH3  The fraction of total number of molecules of any
 H2O < H2S < H2Se < H2Te electrolyte which exists in dissociated state at
 HF < HCl < HBr < HI equilibrium is called degree of dissociation of that
(In PT, strength of hydracids  T2B) electrolyte.
 For strong electrolyte,   1
 For weak electrolyte,  is always less than 1.
Factors Affecting Acidic  Very weak electrolyte  << 1.
Strength of Oxyacid (H m YO n )  Concentration  1/
 Temperature  
 Strength  E.N. of Y (nonmetal)  Addition of common ion suppresses degree of
Example: dissociation. (Common ion effect)
 H2SO3 > H2SeO3
 HClO4 > HBrO4 > HIO4
 H2CO3 < HNO3 Ostwald Law of Dilution
 H2SO4 > H2SeO4
 At constant temperature the degree of
dissociation () of a weak electrolyte is inversely
 Strength  O.N. of Y (when same nonmetal) proportional to the square root of the concentration of
Example: the solution, i.e. decrease in concentration of the
 H2SO3 < H2SO4 solution results in the increase in the degree of
 HNO3 > HNO2 dissociation.
 HClO4 > HClO3 > HClO2 > HClO  Mathematical expression
AB A+ + B –
N.B. 1 0 0
Exception: H3PO2 > H3PO3 > H3PO2 C(1 - ) C C

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 Ionic Equilibrium
 E.g. H3PO4  H+ + H2PO4–; Ka1
if K < 10-5
H2PO4–  H+ + HPO42–; Ka2
1-=1
HPO42–  H+ + PO43– ; Ka3
then K = C2
K  Ka1 > Ka2 > Ka3
[A+][B-] CC C or,  =
K=
[AB]
= =
C(1 - ) (1 - ) C  Kb1 > Kb2 > Kb3

if K < 10-5
1-=1-
C Dissociation of Water
then K = (1 - )
or, C2 + K - K = 0  The dissociation of H2O is an endothermic
-K K2 + 4KC reaction.
or,  =
2C  Water is a weak electrolyte & ionizes to very
small extent.
 This law is only applicable to weak electrolyte.  H2O  H+ + OH–
 K = [H+][OH–]/[H2O]
 Kw = K x [H2O] = [H+][OH–]
N.B.
 For pure water electrical conductivity
=√ experiments give a Keq value of 1.8 x 10–16 M at
25°C.
Hence, (55.5 M)(1.8 x 10–16 M) = [H+][OH¯]
or
Dissociation of Weak Monobasic –16
99.9 x 10 M2 = [H+][OH¯]
Acid or
1.0 x 10–14 M2 = [H+][OH¯]
 HA(aq)  H+ (aq) + A– (aq)
[ ]
 At 25oC, Kw = 1 x 10–14 mol2/L–2
 Ka =  At any temperature the concentration of H+ and
 Greater the value of Ka, stronger is the acid. OH– are found to be equal.
 Greater the value of pKa, weaker is the acid. Therefore, [H+] = [OH–] = Kw= 10–7 mol/L at 25oC
 [H+] = C = = √  pkw = 14
 Kw  Temperature
 Relative strength of two acids of same
concentration = √
pH
Dissociation of Weak Monoacidic  Proposed by Sorensen
 pH = potenz hydrogen ion (potenz = German
Base word means power)
 BOH  B+ + OH–  Defined as negative logarithm of hydrogen ion
[ ] activity ( ).
 Kb =  pH = – log
 Greater the value of Kb, stronger is the base.  =  x [H+], where  is activity coefficient.
 Greater the value of pKb, weaker is the base.  For dilute solution  is 1.
 [OH–] = C = = √  For higher concentration  is less than 1.
 Relative strength of two acids of same  pH = –log [H+]eq
 [H+] = 10–pH
concentration = √  pH = 7 or pOH = 7 or pKw/2  neutral solution
 pH > 7 or pOH < 7  basic solution
 pH < 7 or pOH > 7  acidic solution
Dissociation of Weak Polybasic  pH can be (-)ve for very very concentrated acid.
 pH can be greater than 14 for very very
Acid concentrated base.
 pH is most useful for dilute solution.
 Polybasic dissociated in a number of steps.

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 Ionic Equilibrium
 0 < pH  pKw  Buffers are aqueous systems that resist changes
 pOH = –log[OH–]eq in pH when small amounts of acid or base are
 [OH–] = 10–pOH added. Buffer solutions are composed of a weak
 pKw = –log Kw = –log 10–14 = 14 acid (the proton donor) and its conjugate base (the
 pH + pOH = pKw proton acceptor).
 pH + pOH = 14.  It is of two types
 Ka x Kb = Kw (only for CAB pair) (i) Acidic buffer – Mixture of weak acid and its
 pKa + pKb = pKw = 14 (only for CAB pair) salt
 pH of strong acid or bases does not depend upon (ii) Basic buffer – Mixture of weak base and its
temperature. salt
 pH of weak acid is inversely proportional to
temperature.
 pH of weak base is directly proportional to
Acidic Buffer
temperature.
 pH does not represent the strength of acid or  Buffer mixture of a weak acid and its salt.
base.  E.g. CH3COOH  CH3COO– + H+
 pH of polyprotic acid is only calculated by first CH3COONa  CH3COO– + Na+
deprotonation equilibrium, i.e., Ka1 (except H2SO4).  When small amount of an acid is added, the H+
 pH   [OH–] ions immediately combines with CH3COO– ions to
 If [H]+ increases 10x times, then pH decrease x form weakly dissociated CH3COOH. This H+ ion
unit. concentration does not change, hence, no change in
 If [H]+ decreases 10x times, then pH increases x pH.
unit.  CH3COO– + H+  CH3COOH
 When a few drops of base is added the OH– ions
are neutralized by CH3COOH present in the
N.B.
mixture. Thus OH– concentration does not change
 pH of boiling water = 6.14 and there is no change in the pH.
 At human body temperature(37oC), neutrality  CH3COOH + OH–  CH3COO– + H2O
occurs at 6.8, i.e., pH range is 0 – 13.6

Basic Buffer
Common Ion Effect  Buffer mixture of a weak base and its salt.
 E.g. NH4OH  NH4+ + OH–
 Degree of dissociation of weak electrolyte is NH4Cl  NH4+ + Cl–
suppressed if another electrolyte having a common  If a few drops of an acid is added, the H+ ions of
ion is added to it. the acid combines with NH4OH.
 AB  A+ + B–  NH4OH + H+  NH4+ + H2O
If we add AC, then AC  A+ + C–  If a few drops of base is added, the OH– ion
A+ ion is common ion and concentration of A+ combines with NH4+ ion to form NH4OH which is
ion increases. Applying Le-Chatelier’s principle weak.
concentration of AB will increase i.e. the degree of  NH4+ + OH–  NH4OH
dissociation of AB will be suppressed.  Hence there is no change in concentration of H +
and OH–. Thus the value of pH doest not change.
N.B.
When a strong base is added to an aqueous solution pH of Buffer Solution
of weak acid, the degree of dissociation of acid
increases, this effect is known as reverse ion effect (Henderson’s Equation)
 pH = pKa + log (acidic buffer)
Buffer Solution  pH of acidic buffer can be 7, < 7 or > 7

Cool Chemistry 9051122547/9339228404 5

 Ionic Equilibrium
 pH = 14 – pKb – log (basic buffer) concentration of the ions raised to the power equal to
the number of times the ion occurs in the equation.
 pH of basic buffer can be 7, < 7 or > 7
 In a buffer system when the concentration of
acetic acid and acetate ions are equal, addition of Ionic Product (Q)
small amounts of acid or base do not have any
detectable influence on the pH. This point is  The ionic product (Q) is the product of the
commonly known as the isoelectric point (pI). At concentration of the ions in any solution (may be
this point there is no net charge and pH at this point saturated or unsaturated)
is equal to pKa.  The solubility product (Ksp) is the product of the
 pI = concentration of the ions in saturated solution.
 Q = Ksp ( in case of saturated solution)
 Most simple buffers work effectively in the pH
scale of pKa ± 1.0.
Application of K sp
Buffer capacity () # Determines Solubility
 Let S is the solubility of AxBy in moles/litre.
 Buffer capacity of a buffer is the number of  In general AxBy  xAy+ + yBx–
moles of acid or base added in one litre of solution S xS yS
to change its pH by unity.
 Ksp = [Ay+]x[Bx–]y = (xs)x.(ys)y
  = no of moles of acid or bases added to one = xxSx.yySy = xxyySx+y
litre of buffer/change in pH.
 S=( )
Buffer in Human Blood  Ksp  Solubilty
 Type AB: Ksp = S2
 pH of human blood is 7.4.  Type AB2/A2B = 4S3
 Human blood exhibit buffer nature due to the  Type AB3/AB3 = 27S4
presence of bicarbonate (HCO3–) and carbonic acid  Type A2B3/A3B2 = 108S5
(H2CO3).
 If any acid (H+) enters the blood from outside, it # Determines Solubility in Presence of
is neutralized by HCO3– Common Ion
HCO3– + H+  H2CO3
 AB  A+ + B–
 If any base (OH–) enters the blood, it get
S S S
neutralized by H2CO3.
H2CO3 + OH–  HCO3– + H2O AC  A+ + C–
xM x x
–
Ksp = [A ][B ] = (S + x) S [x >>>> S][S + x 
+

Solubility Product (K s p ) x] = x.S

In presence of common ion solubility decreases.
 Mainly applicable to saturated solution of
 AB2  A2+ +2B–
sparingly soluble salt.
 AgCl (s)  Ag+ (aq) + Cl–(aq) S S 2S
Sparingly soluble salt CB2  C2+ + 2B–
 K = [Ag+][Cl–]/[AgCl] {[AgCl] = constant} xM x 2x
 Ksp = [Ag+][Cl–] Ksp = [A ][B–]2 = S(2S + 2x)2
2+
[x >>>> S]
Solubility product
= 4x2S [2S + 2x  2x]
 In general AxBy  xAy+ + yBx– SSS Strong Ksp
 Ksp = [Ay+]x[Bx–]y Electrolyte
 Thus, the solubility product of a sparingly AB AC Sx
soluble salt forming a saturated solution in water at a AB2 AC2 4S2x
given temperature is given by the product of the AB2 CB2 4Sx2
AB3 AC3 27S3x

Cool Chemistry 9051122547/9339228404 6

 Ionic Equilibrium
AB3 CB3 27Sx3
A2B3 A2C3 108S3x2
A2B3 B2C3 108S2x3
# Prediction of Precipitation
 If Q < Ksp  then solution is unsaturated in
which more solute can be dissolved.
 If Q = Ksp  then solution is saturated in which
no more solute can be dissolved.
 If Q > Ksp  then solution is supersaturated
and precipitation takes place.
 Rate of precipitation 
Qualitative Analysis
# Group I
 1st analytical group of cations consists of ions
that form insoluble chlorides.
 The group reagent to separate them is
hydrochloric acid, usually used at a concentration of
1–2 M. Concentrated HCl must not be used, because
it forms a soluble complex ion ([PbCl4]2-) with Pb2+.
Consequently the Pb2+ ion would go undetected.
 NH3 is also included in ZERO group of cation
(according to NCERT textbooks).
 The most important cations in 1st group are Ag+,
Hg2+2, and Pb2+.
 The chlorides of these elements cannot be
distinguished from each other by their colour - they
are all white solid compounds.
# Group II
 The 2nd analytical group of cations consists of
ions that form acid-insoluble sulfides.
 Cations in the 2nd group include: Cd2+, Bi3+,
Cu2+, As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ and Hg2+. Pb2+
is usually also included here in addition to the first
group.
 Although these methods refer to solutions that
contain sulfide (S2-), these solutions actually only
contain H2S and bisulfide (SH-).
 Sulfide (S2-) does not exist in appreciable
concentrations in water.
# Group III
 3rd analytical group of cations includes ions that
form hydroxides which are insoluble even at low
concentrations.
 The reagents are similar to these of the 2nd group,
but separation is conducted at pH of 8–9.
 Cations in the 3rd group are Fe2+, Fe3+, Al3+, and
Cr3+.
Cool Chemistry 9051122547/9339228404
 The group is determined by making a solution of
the salt in water and adding ammonium chloride and
ammonium hydroxide. Ammonium chloride is added
to ensure low concentration of hydroxide ions.
# Group IV
 The fourth group of cations include Zn2+, Ni2+,
Co2+, and Mn2+.
 Of these, Zinc salts are colourless, Manganese
salts are faint pink or colourless, and Nickel and
cobalt salts may be brightly coloured, often blue-
green.
 The precipitate, washed in water is reacted with
extremely dilute hydrochloric acid. This precipitates
nickel salts, if any.
 The supernatent liquid is filtered and reacted
with excess of Sodium Hydroxide. This precipitates
any Manganese salts.
 Hydrogen sulphide is passed through the
supernatent liquid. If a white precipitate forms, Zinc
is present.
# Group V
 Ions in 5th analytical group of cations form
carbonates that are insoluble in water.
 The reagent usually used is (NH4)2CO3 (at around
0.2 M), with a neutral or slightly basic pH.
 All the cations in the previous groups are
separated beforehand, since many of them also form
insoluble carbonates.
 The most important ions in the 5th group are
Ba2+, Ca2+, and Sr2+.
 After separation, the easiest way to distinguish
between these ions is by testing flame colour: barium
gives a yellow-green flame, calcium gives orange-
red, and strontium, deep red.
Solubility Product of a Weak
Electrolyte
Let degree of ionization of weak electrolyte AxBy be
'α'.
AxBy xAy+ + yBx–
t=0 S 0 0
teq S – Sα xsα ysα
 Ksp = [Ay+]x[Bx–]y
= [xsα ]x[ysα]y
= xxyy (sα)x+y
7
 Ionic Equilibrium
Simultaneous Solubility Acid-Base Indicator
 Acid - Base indicator are weak organic acids or
 Solubility of two electrolytes having common ion; bases which exhibit a sharp colour change at the end
when they are dissolved in the same solution, is point of a titration.
called simultaneous solubility, e.g., Acid & Base Indicator
(i) Solubility of AgBr and AgSCN, when dissolved SA + SB Any indicator
together.
WA + WB No indicator
(ii) Solubility of CaF2 and SrF2, when dissolved
together. WA + SB Phenolphthalein
(iii) Solubility of MgF2 and CaF2 when dissolved SA + WB Methyl orange
together.
Indicator pH Range
N.B. Indicator Colour in Colour pH
Calculation of simultaneous solubility is divided into
acidic in basic range
two cases.
medium medium
Case I: When the two electrolytes are almost
Phenolphthalein Colourless Pink 8.2-10
equally strong (having close solubility product), e.g.,
AgBr (Ksp = 5 x 10-13); AgSCN (Ksp = 10-12) Thymol blue Yellow Blue 8-9.6
Here, charge balancing concept is applied. Phenol blue Yellow Red 6.8-8.4
Charge of Ag+ = Charge of Br- + Charge of SCN- Methyl red Red Yellow 4.2-6.3
Case II: When solubility products of two Methyl orange Red Yellow 3.1-4.4
electrolytes are not close, i.e., they are not equally
strong, e.g.,
CaF2 (Ksp = 3.4 x 10-11); SrF2 (Ksp = 2.9 x 10-9) pH of Acidic Indicator
Most of fluoride ions come of stronger electrolyte.
 HIn  H+ + In–
[ ]
 KIn =
Hydrolysis of Salt n
 pH = pKln + log
n]
 Reverse of neutralistaion.  During change of colour, i.e., at the neutral point,
BA + H2O  HA + BOH [In ] = [ n] or, pH = pKln
Salt Acid Base

 Two types
B+ + H2O  BOH + H+ (cationic hydrolysis) pH of Basic Indicator
A– + H2O  HA + OH– (anionic hydrolysis)
 InOH  In+ + OH–
 Degree of hydrolysis (h) – defined as the fraction [ ]
of total number of mole of that salt hydrolyzed in its  KIn =
aqueous solution at equilibrium. n
 pOH = pKln + log
n ]
n
Salt Kh h pH  pH = 14 – pKln – log
n ]
SA+SB - - 7 N
WA 7 + ½ [pKa + logC] B
+ √ Ostwald's Theory
SB
SA 7 – ½ [pKa + logC] A
+ √  The colour change of any indicator is due to its
WB ionisation. The unionised form of indicator has
WA 7 + ½ [pKa – pkb] N/ different colour than its ionised form.
+ √ A/
 An inidicator is either a weak acid or base, so its
WB B
ionisation is highly affected in acids and bases.

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 Ionic Equilibrium
 If an indicator is a weak acid, its ionisation
would be very much low in acids due to common
H+ ions while it is fairly ionised in alkalies.
 In the same way, if the indicator is a weak base,
its ionisation is large in acids and low in alkalies due
to common OH- ions.
 According to quinonoid theory, an acid-base
indicators exist in two tautomeric forms having
different structures which are in equilibrium. One
form is termed benzenoid form and the other
quinonoid form.

Ostwald Theory of
Phenolphthalein
 The two forms have different colors. The color
 Let phenolphthalein = HPh.
change is due to the interconversation of one
 This indicator being a weak acid ionises in tautomeric form into other. One form mainly exists in
solution to a small extent as follows:
acidic medium and the other in alkaline medium
 HPh H+ + Ph-  Thus, during titration the medium changes from
Colourless Pink acidic to alkaline or vice-versa. The change in pH
 The undissociated molecules converts one tautomeric form into other and thus, the
of phenolphthalein are colourless while the Ph- ions colour change occurs.
are pink in colour. In presence of an acid , ionisation  Phenolphthalein has benzenoid form in acidic
of HPh is practically negligible as the equilibrium medium and thus, it is colourless while it has
shifts to left hand side due to high concentration of quinonoid form in alkaline medium which has pink
H+ ions. Thus, the solution would remain colourless. colour.
 On addition of alkali, hydrogen ions are removed
by OH- ions in the form of water molecules and the
equilibrium shifts to right hand side. Thus, the
concentration of Ph- ions increases in solution and
they impart pink colour to the solution.

Ostwald Theory of Methyl

Orange
 Let methyl orange = MeOH.
 It is a very weak base and ionized in solution to
give Me+ and OH- ions.  Methyl orange has quinonoid form in acidic
 MeOH Me+ + OH- solution
Yellow Red and benzenoid form in alkaline solution. The color of
 In presence of an acid, OH- ions are removed in benzenoid form is yellow while that of quinoniod
the form of water molecules and the above form is red.
equilibrium shifts to right hand side. Thus, sufficient
Me+ ions are produce which impart red colour to the
solution.
 On addition of alkali, the concentration of OH-
ions increases in the solution and the equilibrium
shifts to left hand side, i.e., the ionisation of MeOH is
practically negligible. Thus, the solution acquires the
colour of unionised methyl orange molecules, i.e.,
yellow. N.B.
 The term "equivalence point" means that the
solutions have been mixed in exactly the right
Baeyer’s Quinonoid theory proportions according to the equation.
 At equivalence point, pH of solution represents
the pH of salt.

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 Ionic Equilibrium
 The term "end point" is where the indicator √
changes colour. As you will see on the page about [OH–] =
indicators, that isn't necessarily exactly the same as
C2 = conc of strong base
the equivalence point.
C1 = conc of weak base

# Category 9: pH of Buffer
Types of Different Categories of
 pH = pKa + log (acidic buffer)
Question for pH  pH = 14 – pKb – log (basic buffer)
# Category 1: pH of SA or SB ([H+] or [OH–] > 10–7)
 [H+] or [OH–] = N = M x nf # Category 10: pH of aqueous salt
Salt Kh h pH
# Category 2: pH of WA or WB ([H+] or [OH–] > 10–7) SA+SB - - 7 N
 [H+] = C = =√ WA 7 + ½ [pKa + logC] B
+ √
 [OH–] = C = =√ SB
SA 7 – ½ [pKa + logC] A
# Category 3: pH of SA or SB or WA or WB + √
([H+] or [OH–] < 10–7) WB
WA 7 + ½ [pKa – pkb] N/
 [H+] = 6.96 – 6.99  7 + A/
√
 [OH–] = 7.01 – 7.04  7 WB B
At equivalence point, pH of solution represents the
pH of salt .
# Category 4: Mixture of SA or SB
 When two or more strong acids are mixed # Category 11: pH of Cell
∑
+
[H ] = =  The reduction reaction can be written either as
∑
2H+ + 2e– → 2(g) or H2O + 2 e– → 2(g) + 2 OH–
These two reactions are equivalent and follow the
 When two or more strong bases are mixed
∑ same Nernst equation
[OH–] = = ∑
= + ln ( )
# Category 5: Mixture of SA or SB
which, at 25°C and unit H2 partial pressure reduces to
 When two or more weak acids are mixed
E = E° - (.059/2) × 2 pH = –0.059 pH
[H+] = √ or [H+] = √∑
pH = [ in this case reference half cell
 When two or more weak acids are mixed is calomel electrode]
[OH–] = √ or [OH–] = √∑
# Category 12: pH of aq. Solution of
# Category 7: Mixture of SA & WA amphiprotic salt/ion
When one WA and SA is mixed
pH =
√
[H+] = Example Amphiprotic Salt or Ion:
NaHS or HS–
C2 = conc of strong acid
NaHCO3 or HCO3–
C1 = conc of weak acid
NaH2PO4 or H2PO4–
Na2HPO4 or HPO4–
# Category 8: Mixture of SB & WB
When one WB and SB is mixed
Example: pH of HCO3–
H2CO3 H+ + HCO3– ; Ka1

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 – + –2
Ionic Equilibrium
HCO3 H + CO3 ; Ka2 pH = (for acidic AA)
pH =
pH = (for basic AA)

Example: pH of H2PO4– & HPO4–

# Category 14: pH of Indicator
H3PO4  H+ + H2PO4–; Ka1
H2PO4–  H+ + HPO42–; Ka2  pH of acidic Indicator
n
HPO42–  H+ + PO43– ; Ka3 pH = pKln + log
n]

= During change of colour, i.e., at the neutral point,

[In ] = [ n] or, pH = pKln
=  pH of basic Indicator
n
pOH = pKln + log
n ]
# Category 13: pH of Zwitter ion
n
pH = (for neutral AA) pH = 14 – pKln – log
n ]

# Category 15: pH of Mixture of Acid & Base (Titration)

Acid-Base Condition pH Formula to be used
determining
species
Eq. of SA > Eq. of SB SA ∑ ∑ ∑ ∑
[H+] = ∑ = ∑
SA + SB
Eq. of SA = Eq. of SB Water pH = 7
Eq. of SA < Eq. of SB SB ∑ ∑ ∑ ∑
[OH–] = ∑ = ∑
Eq. of SA > Eq. of WB SA ∑ ∑ ∑ ∑
[H+] = ∑
= ∑
SA + WB
Eq. of SA = Eq. of WB Salt of SA & pH = [pKw – pKb – log C]
WB
Eq. of SA < Eq. of WB Basic Buffer pH = 14 – pKb – log
Eq. of WA > Eq. of SB Acidic Buffer pH = pKa + log
WA + SB
Eq. of WA = Eq. of SB Salt of WA & pH = [pKw + pKa + log C]
SB
Eq. of WA < Eq. of SB SB ∑ ∑ ∑ ∑
[OH–] = ∑
= ∑
Eq. of WA > Eq. of Acidic Buffer pH = pKa + log
WA + WB WB
Eq. of WA = Eq. of Salt of WA & pH = [pKw + pKa – pKb]
WB WB
Eq. of WA < Eq. of Basic Buffer pH = 14 – pKb – log
WB

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