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C-07:- EQUILIBRIUM
1. EQUILIBRIUM
An equilibrium represents a state in a process when the EXAMPLE:1 During bottling a carbonated beverage was made by
observable properties such as colour, temperature, pressure, CO2 at a pressure of 4.0
concentration etc. do not show any change. saturating flavoured water at 00C with
A. Types of equilibrium atm. Later, the bottle was opened and the soft drink is allowed to
Equilibrium is of two types
i. Physical equilibrium ii. Chemical equilibrium come at equilibrium at 250 C with air containing CO2 at a
Physical equilibrium
Equilibrium in physical processes is called physical equilibrium.
B. Chemical equilibrium pressure of 4.0 101 atm. Find the concentration of CO2
Equilibrium associated with chemical reaction is known as
in the freshly bottled soda and in the soda after it had stood open
chemical equilibrium.
and come to equilibrium. The Henrys constant for aqueous
Types of physical equilibrium
Physical equilibrium is of three types
solution of
CO2 are
i. Solid-liquid equilibrium
Ice water 00 C , k =7.7 102 mol L1 atm1
At
Rate of melting = Rate of freezing
At 250 C , k =3.2102 mol L1 atm1
ii. Liquid-gas equilibrium
Water vapours SOLUTION: For opened bottled soft drink.
Rate of vaporisation = Rate of condensation
iii. Solid-gas equilibrium C=kP=( 7.7 102 mol L1 atm1) ( 4.0 atm )=0.308 mol L
It occurs only in those solids which sublimise on heating.
For example: Ammonium chloride, iodine, camphor. For freshly bottled soft drink
NH 4 C l ( s ) NH 4 C l(g) C=kP
2. EQUILIBIUM RELATING TO DISSOLUTION OF C=( 3.2 102 mol L1 atm1 ) ( 4.0 104 atm )
SOLIDS IN LIQUIDS OR GASES IN LIQUIDS
Equilibrium between a solid and its solution is indicated by 1.28 105 mol L1
saturated solution.
Solubility 3. SOME GERNERALISATIONS ASSOCIATED WITH
The maximum amount of the solute in grams which dissolves in PHYSICAL EQUILIBRIA
100 g of the solvent at a given temperature to form the saturated
A. Solid liquid equilibrium is obtained only at a particular
solution is known as the solubility. Solubility of the solid in
solution is constant at constant temperature. temperature. This temperature is the melting point of solid of freezing
The equilibrium may be represented as point of the liquid.
Sugar (in solution) Sugar (solid) B. In liquid gas equilibrium, the pressure of the vapours of the
Equilibrium between a gas and its solution in a liquid liquid above the liquid surface is called vapour pressure. It is constant
The equilibrium may be represented as at a given temperature. At equilibrium the molecules in two phases
CO2 ( g) CO 2 (present in solution) have equal kinetic energy. Addition of salt flowers the vapour pressure.
Some features of physical equilibrium
(Note)
Henrys law Process Conclusion
The mass of gas that dissolve in a given mass of a solvent at any
temperature is proportional to the pressure of the gas above the Liquid Vapour PH O
2 constant at given
surface of the solvent. Mathematically,
m p or m=k p (k is a constant) H 2 O(l) H 2 O(g) temperature
H 2 O (s)
H 2 O(l)
B.
P caO .
2
PCaCO 3
PCaCO 3 iii. When the equation is multiplied by 2, the new equilibrium constant
2
PCaO / PCaCO PCO is K .
C. 3 D. 2
iv. When the equation is divided in two steps, the new equilibrium
11. CHARACTERSTICS OF EQUILIBIUM CONSTANT
A. Variation of K with temperature constant is
K=K 1 K 2
Equilibrium constant varies with temperature. Its variation
with temperature can be described by the following relation The value of equilibrium constant gives an idea about the extent to
which a reaction has processed at a given temperature before
log
K2
=
[
H T 2T 1
K 1 2.303 R T 1 T 2 ] equilibrium. is attained.
E. Estimation of extent of reaction:
Numerical value of equilibrium constant reflects that how far the
Where H= Enthalpy change, K 1 and K 2= reaction proceeds before the equilibrium state is reached.
3
If K c >10 , products predominate over reactants. If K c is
Eequilibrium constant at temperature
T 1 and T 2
very large, the reaction proceeds nearly to the completion.
respectively.
If K c <10
3
, reactants predominate over products. If
K c is
R= Universal gas constant. This equation is known as
very small, the reaction proceeds hardly at all.
Vant Hoff equation.
B. The different form of above equation is iii. If
K c is in the large 103 to 103 , appreciable
dK p H 0
= concentrations of both reactants and products are present.
dT RT 2 EXAMPLE
EXAMPLE:4
Na2 SO 4 . 10 H 2 O( s)
Note
C. Vant Hoff reaction isotherm
Na2 SO 4 ( s )+ 10 H 2 O(g) For the equilibrium,
0
0 C is 4.58 torr, at which relative humidities will 1/2 O2 ( g ) NO 2 ( g ) , K 1
A. NO ( g )+
Na2 SO 4 be deliquescent (absorb moisture) when exposed to
B.
2 NO 2 ( g ) 2 NO ( g ) +O2 ( g ) , K 2
0
the air at 0 C essentially.
The equilibrium constants
K 1 and K 2 are related as
SOLUTION: We have
K p=4.08 1025 A.
K 2=1/ K 1 B.
K 2=K 1 /2
2 2
10
K p=P H O=4.08 10
25
C. K 2=1/ K 1 D. K 2=K 1
2
In case of a weak electrolyte at a given temperature, the degree of Acid : An acid is a substance with sour taste. It turns blue litmus red. It
ionisations is inversely proportional to the square root of the molar liberates hydrogen with active metal like sodium, calcium, magnesium
concentration or directly proportional to square root of the volume of etc.
the solution which contains one mole of the electrolyte. + +
Misconcepts Aqueous solution of an acid is characterized by H 3 O or H
The misconcept is that this law is applicable to all type of
electrolytes. The concept is that it is applicable only to weak ions.
electrolytes. Base : A base is a substance with bitter taste. It turns red litmus blue. It
For weak electrolytes has a soapy touch.
Ca2
; K = Aqueous solution of a base is characterized by OH ions.
1 '
+ +B Three theories have been given to explain acidic and basic
AB A characters of the substances. These are:
A. Arrhenius concept of acids and bases
According to Arrhenius concept of acids and bases, an acid is a
And =
K
C
substance which gives
+
H ions in the aqueous solution whereas a
Where K is known as ionisation constant.
Red Alert
OH ions in the aqueous solution.
Ka base is a substance which gives
For weak acids : =
C i. The relative strengths of weak acids and weak bases are generally
+ compared in terms of their dissociation constants
H Strengthof base 1
And as : For weak acids: Stength of acid 2
= K b .C Strength of base 1 1 K b
and [OH ]
For weak bases: = = 1
strength of base 2 2 K b 2
Ka 100
A. 100 B. ( pKa pH ) acids and bases respectively.
C 1+10 Red Alert
ii. Arrhenius theory is valid for aqueous solutions only.
C. both correct D. none is correct iii. Arrhenius theory does not account for the basicity of
39. Theory of ionization was given by
substances like, ammonia which do not possess a hydroxyl
A. Faraday B. Rutherford
C. Arrhenius D. Graham group.
40. The degree of ionization of a substance +
A. decreases with dilution iv. Expressing H for weak acids
B. increases with dilution
C. may increase or decrease with dilution
D. is not affected with dilution.
18. THEORIES OF ACIDS AND BASES
7
H
All negative ions like F , C l , Br , I , OH
+
, CN etc.
B. Bronsted Lowry concept of acids and bases
ii. aTypes of Lewis acids
According to Bronste-Lowry concept of acids and bases, an acid is
substance which can lose a proton and a base is a substance which canMolecules having central atom with incomplete octet For example:
accepts a proton. BF 3 , A lC l 3 etc.
i. Conjugate acid-base pair: An acid-base pair which differs by a
+ 2+ 3+
proton is called conjugate acid-base pair. Conjugate acid Simple cations. For example : Ag , Cu , Fe etc.
+
Conjugate base + H . Molecules having central atom with empty d - orbitals for
example:
SnC l 4 , SiF 4 , PF 5 , FeC l 3 etc.
ii. Amphoteric substance: A substance which can act both as an acid Molecules containing multiple bonds between different atoms. For
as well as base in different reactions is called amphoteric substance. O=C=O .
Water has dual role. In case of reaction with HCl water acts as a base example:
while in case of ammonia it acts as an acid by donating a proton. EXCEPTIONS
Bronsted Lowry concept is applicable to both aqueous as well as non H 2 SO 4 is a strong acid but it can even act as a base. This is
aqueous solutions.
Red Alert H 2 SO 4 is mixed with another acid which is
Comparison of relative strength of acids and bases. possible, when
i. A strong acid has a weak conjugate base and vice versa. Similary, a
stronger than it.
strong base has a weak conjugate acid and vice versa. For example : Misconcepts
Increasing order of acidic strength is The misconcept is that pH value for acid can be more than 7. The
HC l O< HC lO2 < HC l O3 < HC lO4 . HC l O4 is the 10
8
concept is for M HCl solution, pH is not 8, because acid
strongest acid and HC l O is a weakest acid. Order of strength solutions always have pH < 7. For this solution, pH=6.96.
For weak acid/base, the pH shall depend on its degree of ionisation.
of their respective conjugate bases is For example, pH of weak acid HA is given as
>C l O 4 ++ A
>ClO3
HA H
hence C lO is the strongest base.
>C l O 2
equivalent conc. C ( 1 ) C C
C lO
H
ii. A base in contact with a strong acid behaves as a strong base while a
base in contact with a weak acid behaves as a weak base. +
Note
Comparison of Bronsted-Lowry and Arrhenius concepts
i. All Arrhenius acids are Bronsted acids.
ii. All Arrhenius bases are not Bronsted bases. pH=log [C ]
C. Lewis concept of acids and bases
According to Lewis concept of acids and bases, an acid is a Also since
K a of weak acid C 2
substance which can accept a pair of electrons whereas a base is a
substance which can donate a pair of electrons. H
i. Types of Lewis bases
1. Neutral molecules containing a lone pair of electrons on the central +
atom like
NH 3 , PH 3 , ROH , H 2 O etc. K a / =C=
8
Salts formed by incomplete neutralisation of poly acidic bases which An indicator is a substance which is used to determine the end point in
still contain one or more hydroxyl groups. a titration. pH indicators are either weak acids or weak bases.
Zn ( OH ) C l , Mg ( OH ) C l etc . Two theories have been proposed to explain the change of colour of
For example:
indicators.
C. Mixed salts give more than one anions or cations on dissolving in A. Ostwalds theory
According to this theory the colour change is due to ionisation of the
water. For example: CaOC l 2 acid-base indicator. The unionised
Sr.No. Indicator pH range Colour change form has different colour than the
ionised form.
1. Methyl orange 3.24.5 Pink to yellow
gives C l and OC l . B. Quinonoid theory
According to this theory
2. Methyl red 4.46.5 Red to yellow
Red Alert the acid-base indicators exist in
When a salt is dissolved in water to 3. Red litmus 5.57.5 Red to blue two tautomeric forms having
produce ions, the process is always different structures benzenoid
endothermic since energy is required 4. Phenol red 6.88.4 Yellow to Red form and quinonoid form. These
to break salt into ions. two forms have different colours.
Check Your Grasp 5. Phenolphthalein 8.310.5 Colourless to pink Note
57. When
NH 4 C l is added to a The colour change and the
pH range of some common indicators
solution of-
NH 4 OH Red Alert
The suitable indicators of the following titrations are
A. Strong acid versus strong base Phenolphthalein,
A. only the concentration of OH ions increases methyl red and
methyl orange
B. Weak acid versus strong base Phenolphthalein
B. only the concentration of OH ions decreases C. Strong acid versus weak base Methyl red and methyl orange.
+ - Methyl red and
C. the concentration of NH 4 ions decreases methyl orange.
D. Weak acid versus weak base No suitable indicator.
+ E. During titration with
KMnO 4 , no indicator is used because
D. the concentration of NH 4 as well as OH ions
KMnO 4 is a self indicator.
decreases.
Check Your Grasp
61. The pH indicators are
58. Which one of the following is acid salt? A. salt of strong acids and strong bases
A.
Na 2 S B.
Na 2 SO 3 B. salts of weak acids and weak bases
C. either weak acids or weak bases
NaHSO3 Na 2 SO 4 D. either strong acids or strong bases.
C. D.
59. Which one is not an acid salt?
NaH 2 PO 4 Na 2 HPO4 62. Identify the indicator used to litrate
Na2 CO 3 solution with
A. B.
C. NaCl D. Both (a) and (b) HC l
60. Neutralization of an acid with a base, invariably results in the
production of A. phenolphthalein B. dilute
H 2 SO 4
+
A. H 3 O B.
H2O C. methyl orange D. none
26. SALT HYDROLYSIS
+ Hydrolysis is a process in which a salt reacts with water to form acid
C. H and OH D. OH and base.
acid + base
26. ROLE OF INCDICATOR IN ACID-BASE TITRATION Salt + water
(VOLUMETRIC ANALYSIS) Salt hydrolysis is reverse of neutralisation reaction.
Types of salt hydrolysis
There are four cases of salt hydrolysis. These are as follows:
10
soluble.
10
A gCl( K sp =1.7 10 ) ++C l
H
C l H
K
13
A ( sp=7.7 10 )
g Br The concentration of C l ions increases due to ionization of
A 2 B type +
B. For RCOO
conc. of Na ions. Thus, the ionic product of
S 3
K sp
4 +
Na exceeds the solubility product of soap and, therefore, soap
C. For
AB 3
K sp precipitates out from the solution. This is called salting out of soap.
S 4 EXAMPLE
27 Ca
D. For
A 3 B2 type PO
EXAMPLE:4 If the solubility of calcium phosphate is a
S 5
K sp
108
Where A is cationic part and B is anionic part. And S is the mol L1 , the solubility product is equal to
K sp is solubility product constant.
solubility, A. 6 a5 B. 72 a5
C. Cus(Ksp=8 1037)
D. Ag 2 S ( K sp=6 1051)