4.chemical Equilibrium PDF

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Summary
At Equilibrium:
(i) Rate of forward reaction = rate of backward reaction
(ii) Concentration (mole/itre) of reactant and product becomes constant.
(iii) ∆G = 0.
(iv) Q = Keq.
Equilibrium constant (K):
rate constant of forward reaction K f
K =
rate constant of backward reaction K b
Equilibrium constant in terms of concentration (Kc).
Kf [C ]c [ D]d
t
= K=
ne
c
Kb [ A]a [ B]b
Equilibrium constant in terms of partial pressure (Kp).
e.
[ P ]c [ P ]d
Kp = C a D b
[ PA ] [ PB ]
iv
at
• Equilibrium constant in terms of mole fraction (Kx).
re
xCc xDd
Kx = a b
x A xB
nc
• Relation between Kp and Kc

ar
Kp = Kx (RT)∆n.
• Relation between Kp and Kx.
.le
Kp = Kx (P)∆n.
Where P = Total pressure at equilibrium.
w
∆n = (c + d) – (a + b), calculation of ∆n involves only gaseous component.

w
⟹ ∆n = sum of the number of moles of gaseous products – sum of the number of moles of
w
gaseous reactants.
∆n can be positive, negative, zero or even fraction.
• Dependence of Keq on the stoichlometry of the reaction.
(a) If two chemical reactions at equilibrium having equilibrium constant K1 and k2 are added
then the resulting equations has equilibrium constant K = K1 . K2
Equilibrium constant
A⇌B K1
B⇌C K2
On adding A⇌C K = K1 . K2
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(b) If the reaction having eq. constant K1 is reversed then resulting equation has eq. constant
1
K1
A+B ⇌ C+D
1
On reversing, C+D ⇌ A+B K=
K1
(c) If a chemical reaction having equilibrium constant K, is multiplied by a factor n then the
resulting equation has equilibrium constant K =(K1)n, n can be fraction
Eg. D2 ⇌ 2A K1
1 1
Multiplying by   , D2 ⇌A = K (= K1 )1/2 K1
2
  2
t
• Dependence of Keq on Temperature.
ne
Equilibrium constant is only dependent upto the temperature for a given reaction.
It means kp and kc will remain constant at constant temperature no matter how much changes are
e.
made in pressure, concentration, volume or catalyst.
iv
But Kx depends on pressure provided ∆n ≠ 0, i.e. even at constant temperature, kx, will undergo a
change by
at
K ∆H  1 1 
re
• =log 2  −=  ; ∆H Enthalpy of reaction
K1 2.303 R  T1 T2 
nc
If T2 > T1 . Then K 2 > K1 provided ∆H = + ve (endothermic reaction)

K 2 < K1 if ∆H = -ve (exothermic reaction)
ar
In the above equation, the unit of R and ∆H should be same.

.le
• Relation between equilibrium constant & standard free energy change

∆Go = -2.303 RT log K
w
Where ∆Go = standard free energy change

w
T = Absolute temperature,
w
R = Universal gas constant.

• Significance of value of Equilibrium constant (k):
How to use neglection in the problem:
[ Product ]
K=
[Re actant ]
Case . I
If K is large (k > 103) then product concentration is very very larger than the reactant
([Product]>>[Reactant)) can be neglected with respect to the product. In this case, the reaction is
Hence concentration of reactant ' product favourable and equilibrium will be more in forward
direction than in backward direction.
Case . II

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If K is very small (K < 10 3)

[Product] << [Reactant]
Hence concentration of Product can be neglected as compared to the reactant. In this case, the
reaction is reactant favourable.
Reaction Quotient (Q):

[C ]c [ D]d
The values of expression Q = at any time during reaction is called reaction quotient
[ A]a [ B]b
If Q > Kc reaction proceed in backward direction until equilibrium in reached
If Q < Kc reaction will proceed in forward direction until equilibrium is established
If Q = Kc Reaction is at equilibrium
Degree of Dissociation (α):
t
ne
Α = no. of moles dissociated / initial no. of moles taken
= fraction of moles dissociated out of 1 mole.
e.
Note: % dissociation = α × 100
• Observed molecular weight and Observed Vapour Density of the mixture
Observed molecular weight of An ( g ) =
iv
molecular weight of equilibrium mixture
at
total no. of moles
re
M th
∴ M obs =
[1 + (n + 1)α ]
nc
M An
D = vapour density without dissociation =
ar
2
M mix
.le
d = vapour density of mixture = observed v. d =

2
D
w
=1 + (n − 1)α
d
w
D−d MT − M o
α =
w
=
(n − 1) × d (n − 1) M o
where M1 = Theoretical molecular wt. Mo = observed molecular wt. or molecular wt. of the
mixture at eq.
Note: It is not applicable for n = 1 [eg. Dissociation of HI & NO].
Significance of n:
sum of stoichiome tric coeff of product

n=
sum of coeff of reac tan ts
Ex. PCl 5  PCl3 + Cl2

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α 2 .P
Kp = (Remember)
1−α 2
External Factor Affecting Equilibrium:

Le Chatlier’s Principle:
If a system at equilibrium is subjected to a disturbance or stress that changes any of the factors
that determine the state of equilibrium, the system react in such a way as to minimize the effect
of the disturbance.
Effect of Concentration:
• If the concentration of reactant is increased at equilibrium, then reaction shift in the forward
direction.
• If the concentration of product is increased then equilibrium shifts in the backward direction
t
ne
Effect of Volume:
• If volume is increased pressure decreases hence reaction will shift in the direction in which
e.
pressure in crease that is in the direction in which number of moles of gases increases and
vice versa.
• If volume is increased then,
iv
at
∆n > 0 reaction will shift in the forward direction
re
∆n < 0 reaction will shift in the backward direction
∆n > 0 reaction will not shift.
nc
Effect of Pressure:
ar
• If pressure is increased at equilibrium then reaction will try to decrease the pressure, hence it
.le
will shift in the direction in which less no. of moles of gases are formed.
Effect of Inert Gas Addition:
w
(i) Constant pressure: If inert gas is added then to maintain the pressure constant, volume
is increased, Hence equilibrium will shift in the direction in which larger no. of moles of
w
gas is formed
w
∆n > 0 reaction will shift in the forward direction

∆n < 0 reaction will shift in the backward direction
∆n > 0 reaction will not shift.
(ii) Constant volume: Inert gas addition has no effect at constant volume.
Effect of Temperature:
Equilibrium constant is only dependent upon the temperature.
1 ∆H 0 ∆S 0
If plot of ℓnk vs is plotted then it is a straight line with slope = − , and intercept =
T R R
• For endothermic (∆H > 0) reaction value of the equilibrium constant increase with the rise in
temperature.

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• For exothermic (∆H < 0) reaction, value of the equilibrium constant decreases with increase
in temperature.
• For ∆H > 0, reaction shifts in the forward direction with increase in temperature.
• For ∆H < 0, reaction shifts in the backward direction with increase in temperature.
o Vapour Pressure of Liquid:
It is the pressure exerted by the vapour over it’s liquid when it is in equilibrium with the liquid.
Vapour pressure of water is also called aqueous tension.
H 2O()  H 2O( g );= K p P= H 2O constant at fixed temperature.
Hence V.P. of liquid is independent of pressure, volume and concentration change.
e.g. at 250C, vapour pressure of water ≈ 24 mm of Hg
Partial pressure of H 2O vapours
• Relative Humidity =
Vapour pressure of H 2Oat the temp.
t
ne
Thermodynamics of Equilibrium:
e.
For a general reaction, mA + nB  pC + qD, ∆G is given by –
iv
∆G = ∆Go + 2.303 RT log10Q
∆Go = -2.303 RT log10K
at
∆Go = ∆Ho - T∆So
re
∆H o 1 ∆S o
log10 K
= . +
nc
2.303 RT 2.303R
1 ∆H 0 ∆S 0
If plot of ℓnk vs is plotted then it is a straight line with slope = − , and intercept =
ar
T R R
.le
w
w
w
−∆H o ∆S o
Slope = = tan θ , y intercept =
2.303R 2.303R
K  ∆H o  1 1 
Vant Hoff equation-= log  1   − 
 K 2  2.303R  T2 T1 
Note: * ∆Ho should be substituted with sign.
* For endothermic (∆H > 0) reaction value of the equilibrium constant increases with
the rise

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in temperature.
* For exothermic (∆H < 0) reaction, value of the equilibrium constant decreases with
increase
in temperature
Simultaneous Equilibrium:
If in any container there are two or more than two equilibria existing simultaneously involving
one or more than one common species. Then in both / all the equilibria the concentration of
common species is the total concentration of that species due to all equilibria is taken under
concentration
e.g. A(s) ⇌ x(g) + Y(g) B(s) ⇌ Z(g) + Y(g)
t=0 a 0 0 b 0 0
t = teq a – t t t+u b–u u u +t
t
K= t (u + t ) K c= (u + t )u
ne
c1 2
e.
Ionic Equilibrium
iv
at
Ostwald Dilution Law:
re
[ H + ][ A−1 ] [Cα ][Cα ] Cα 2
o Dissociation constant of weak acid (Ka), Ka = = =
[ HA] C (1 − α ) 1−α
nc
Ka
If α << 1, then 1 − α ≅ 1 or=
K a cα 2 or
= α = Ka ×V
ar
C
1
.le
[C = , then V = 1/C (volume of solution is which 1 mole is present) is called dilution, so

V
α2
w
Ka = ]
(1 − α )V
w
Kb
w
Similarly for a weak base, α = . Higher the value of Ka / Kb, strong is the acid / base.
C
Acidity and pH scale:
∴ pH = aH + (where aH + is the activity of H+ ions = molar concentration for dilute solution).
Activity of H+ ions = molar concentration for dilute solution).
Activity of H+ ions is the concentration of free H+ ions or H3O+ ions in a solution.
[Note: ph can be also be negative or > 14]
pH = − log[ H + ]; [H + ] =
10− ph
− log[OH − ];
pOH = [OH − ] =
10− poH
− log ka;
pKa = 10− pka
Ka =
pkb = − log kb; 10− pkb
Kb =
Properties of Water:

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1. In pure water [H+] = [OH-] so it is Neutral.

2. Moler concentration / Molarity of water = 55.56 M.
3. Ionic product of water (Kw):
H 2O  H + = [OH − ] K w =[H+ ][OH- ]=10-14 at 250 (experimentally)
On increasing temp ⇒ Kw increases (dissociation of water, is endothermic, so on increasing
temperature Keq increases)
Now pH=-log[H+ ]= 7 and pOH=-log[H- ]= 7 for water at 250 (exp).
pH= 7= pOH ⇒ neutral
pH < 7 or pOH > 7 ⇒ acidic
pH > 7 or pOH < 7 ⇒ Basic
Note. Ionic product of water is always a constant whatever has been dissolved in water
since its an equilibrium constant so will be dependent only on temperature.
4. Degree of dissociation of water:
t
ne
no.of moles dissociated 10−7
H 2O  H + + OH − ⇒α = = = 18 ×10−10 or1.8 ×10−7 %
Total No. of moles initially taken 55.55
e.
5. Absolute dissociation of water:
iv
[ H + ][OH − ] 10−7 ×10−7
H 2O  H + + OH − Ka = Kb = = = 1.8 ×10−16
[ H 2O ] 55.55
at
So, pK a = pK b = − log(1.8 ×10−16 ) =
16 − log1.8 =
15.74
re
Note: For a conjugate acid base pairs
nc
K=a K=b [ H + ][OH =

−
] Kw
⇒ pK a = pK b = pK w = 14 at 250C
ar
Note: pK a of H3O+ ions=-1.74

.le
pK b of OH- ions=-1.74
o pH Calculations of Different Types of Solutions:
w
(a) Strong acid solution:

(i) lf concentration is greater than 10-6 M
w
+
In this case H ions coming from water can be neglected,
w
so [H+] = normality of strong acid solution

(ii) If concentration is less than 10-6 M
ln this case H. ions coming from water cannot be neglected and since water is a weak
electrolyte so its dissociation equilibrium will be disturbed much more than dissociation
equilibrium of strong acid.
So [H+] = normality of strong acid + H+ ions coming from water in presence of this strong acid
(b) Strong base solution:

Using similar method as in part (a) calculate first [OH-] × [OH-] = 10-14.
(c) pH of mixture of two strong acids:
lf V1 volume of a strong acid solution of normality N1 is mixed with V1 volume of another strong
acid solution of normality N2, then
Number of H+ ions from l - solution = N1V1,

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Number of H+ ions from l - solution = N2V2,

If final normality is N and final volume is V, then NV = N1 V1 + N2 V2
[dissociation equilibrium of none of these acids will be disturbed as both are strong acid]
N1V1 + N 2V2
[ H +=] N=
V1 + V2
(d) pH of mixture of two strong bases:
similar to above calculation
N1V1 + N 2V2
[OH −= ] N=
V1 + V2
(e) pH of mixture of a strong acid and a strong base:
There will be neutralisation of the acid and the base, and the solution will be acidic or basic
depending
on which component has been taken in excess
t
lf V1 volume of a strong acid solution of normality N1 is mixed with V2 volume of a
ne
strong base
solution of normality N2, then
e.
Number of H+ ions from I – solution = N1V1
Number of OH- ions from II – solution = N2V2
iv N V + N 2V2
If N1V1 > N2V2, then solution will be acidic in nature and [H+] = N = 1 1
at
V1 + V2
re
N V + N 2V2
If N2V2 > N1V1, then solution will be acidic in nature and [OH-] = N = 2 2
V1 + V2
nc
(f) pH of a weak acid{monoprotic) solulion:

[ H + ][OH ] Cα 2
ar
= Ka =
[ HA] 1−α
.le
Ka
If α << 1 ⇒ (1 − α ) ≈ 1 ⇒ K a ≈ Cα 2 α= (is valid if α < 0.1 or 10% )
C
w
Ka
w
+
H= α C
C= = Ka × C
C
w
1
pH
= ( pka − log C )
2
On increasing the dilution ⇒ C ↓⇒ α ↑ and [ H + ] ↓⇒ pH ↑
** At very low concentration (∞ dilution) weak electrolyte will be almost l00% dissociate, so
behave as strong electrolyte.
(g) pH of a solution of a polyprotic weak acid:
[ H ]T =
+
Cα1 + Cα1Cα 2 + Cα1α 2α 3 ≈ Cα1
[Generally, K a3 << K a2 << K a1 ,α 2 and α 3 can be neglected].
1
pH
= ( pka1 − log C )
2
WEAK POLY BASIC ACIDS:
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K1 K2 K3
H 3 PO4   
 H + H 2 PO4 ; H 2 PO4 
+ − −
 2− 2−
 H + H 2 PO4 ; H 2 PO4 
+
  +
 H + PO4
3−
The relative value of these constant is, k1 > k2 > k3

Relative strength of two Acids:
[ H + ] furnished by I acid c1α1 ka 1 c1 ka
= = If acids are highly strong, the relative strength = 1
[ H ] furnished by II acid c2α 2
+
ka 2 c2 ka 2
(h) pH of a mixture of two weak acid (both monoprotic) solutions:
Let the acid are HA1. & HA2 and their final concentrations are C1 & C2 respectively, then
Ka α
Generally, (α1 << 1) and (α 2 << 1) ⇒ 1 = 1
K a2 α 2
**If water is again considered third weak acid in solution of two weak acid then
[H+ ]= K a1C 1 + K a 2C2 + K w
t
ne
−14
K aw 10
Cw= = Kw
[H + ] = C1 K a1 + C2 K a 2 + 10−14
e.
(i) pH of a mixture of weak acid(monoprotic) and a strong acid solution:
iv
If [SA] = C1 and [WA] = C2, then [H+] from SA = C1 and [H+] from WA = C2.
Let HA is a weak acid.
at
Generally, α << 1 . Therefore, K a ≈ (C2α + C1 )α
re
C1 C12 + 4 K a .C2
[H + ] =
nc
2
ar
**If a strong acid of low conc is added in water then [H+] of solution can be calculated as
C C 2 + 4Kw
.le
[H + ] = 1 1
2
o Salt Hydrolysis
w
w
Salt of Type of Kh h ph
hydrolysis
w
(a) weak acid & strong anionic, kw kw 1 1

base 7+ pka + log c
ka ka c 2 2
(b) strong acid & weak cationic kw kw 1 1
base 7− pkb + log c
kb kb c 2 2
(c) weak acid & weak Both kw kw 1 1
base 7+ pka − pkb
k a kb k a kb 2 2
(d) Strong acid & strong -------do not hydrolysed-------- pH = 7
base
Hydrolysis of ployvalent anions or cations

@aakashallen
For [Na3PO4] = C.
K a1 × K h 3 =
Kw
K a1 × K h 2 =
Kw
K a13 × K h1 =
Kw
Generally pH is calculated only using the first step Hydrolysis
Ch2
=K h1 ≈ Ch 2
1− h
K h1 k w × ka 3
h= ⇒ [OH − ] = ch = K h1 × c ⇒ [ H + ] =
c c
So
1
t
pH= [ pK w + pK a 3 + log C ]
ne
2
Hydrolysis of Amphiprotic Anion. (Cation is not Hydrolysed e.g. NaHCO3, NaHS, etc.)
e.
ionisation

(a) (i) HCO3− + H 2O   2−
 CO3 + H 3O
+
acid
iv
hydrolysis
3

(ii) HCO + H 2O 
−
 H 2CO3 + OH
− at
base
 pK a1 + pK a2 
pH ( HCO3− ) = 
re

 2 
nc
(b) Similarly for H 2 PO4 and HPO4 amphiprotic anions.

− 2−
 pK a1 + pK a2   pK a2 + pK a3 
pH ( H PO− ) =  and pH ( H PO2− ) = 
ar
 
2 4
 2 
2 4
 2 
.le
K aT Ka 2 2− K a3 3−
o H 3 PO4 → H 2 PO4 → HPO4 → PO4
−
←
Kw ← Kw ← Hydrolysis (reverse of ionisation)
w
Kw
kh1 = kh1 = kh1 =
ka1 ka2 ka 3
w
1
The pH of H=
3 PO4 ( pka1 − log C ) ∴ ka1 >> ka 2 >> ka 3
2
w
1
pH of NaH=
2 PO4 ( pka1 + pK a 2 )
2
1
pH of Na2=HPO4 ( pka 2 + pK a 3 ) ∴sec ionisation can neglect
2
1
pH of Na3 PO4= ( pkw + pKa + log C ) ∴ See hydrolsis can neglect
2
Buffer Solution:
(a) Acidic Buffer: e.g. CH3COOH and CH3COONa. (weak acid and salt of its conjugate
base).
[ Salt ]
pH pK a + log
= [Henderson's equation]
[ Base]
(b) Basic Buffer: e.g. NH4OH + NH4Cl. (weak base and salt of its conjugate acid.)

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[ Salt ]
= pK a + log
pOH
[ Base]
Buffer capacity (index):
It is the ratio of the small amount of acid or base added to the change in pH caused in the buffer
Total no. of moles of acid / base added per litre
Buffer capacity =
Change in pH
dx (a + x)(b − x)
Buffer capacity = = 2.303
d ∆ρ H a+b
Indicator:
There is equilibrium between the ionised and unionsed form of an acid indictor (HIn)
HIn  H + + ln −
[ H + ][ln − ]
=∴ K HIn = [ K HIn indicator constant or dissociation constant of indicator ]
t
[ HIn]
ne
[ HIn]
or [ H= +
] K HIn × −
[ln ]
e.
[ln − ] [ Ionised form]
iv
∴=pH pK HIn + log ⟹ = pH pK HIn + log
[ HIn] [UnIonised form]
at
SIGNIFICANCE OF INDICATORS:
• Extent of reaction of different bases with acid (HCl) using two indicators:
re
Phenolphthalein Methyl Orange
nc
NaOH 100% reaction is indicated 100% reactions is indicated

ar
NaOH + HCl → NaCl + H 2O NaOH + HCl → NaCl + H 2O

Na2CO3 50% reaction upto NaHCO3 stage 100% reaction is indicated
.le
is indicated Na2CO3 + 2 HCl → 2 NaCl + H 2O + CO2

Na2CO3 + HCl → NaHCO3 + NaCl
w
NaHCO3 No reaction is indicated NaHCO3 + HCl → NaCl + H 2O + CO2

w
w
∎Isoelectric Point: of amino acid is the point when the net charge is equal to zero:
⇒ At isoelectric point, [Anionic form] = [Cationic form]
[ H + ] = K a1 K a2
pK a1 + pK a 2
pH =
2
Solubility Product:
∎ Simple Solubility in water:
The solubility of AxBy in water is ‘s’ M, then
Ax By  xA y + + yB − x
- xs ys ∴ K sp (=
= xs ) x ( ys ) y x x . y y .( s ) x + y
Condition for Precipitation:

@aakashallen
If ionic product K I .P > K sp precipitation occurs,

If K I .P > K sp saturated solution (precipitation just begins or is just prevented).
t
ne
e.
iv
at
re
nc
ar
.le
w
w
w

@aakashallen
Practice Questions
1. For standardizing NaOH solution, which of the following is used as a primary standard?
(2018)
(a) Sodium tetraborate
(b) Ferrous Ammonium Sulfate
(c) Oxalic acid
(d) dil. HCl
2. A white solution salt dissolves readily in water to give a solution which is neutral to litmus.
When silver nitrate solution is added to the before mentioned solution, a white precipitate is
obtained which does not dissolve in dil. Nitric acid. The anion is (2018)
t
(a) Cl −
ne
(b) S 2
e.
(c) SO42−
(d) CO32−
iv
at
3. An alkali is titrated against an acid with methyl orange as indicator, which of the following is a
re
correct combination? (2018)
(a) Base – Strong; Acid – Strong; End point – Pink to colourless
nc
(b) Base – Weak; Acid – Strong; End point – Colourless to pink

(c) Base – Strong; Acid – Strong; End point – Pinkish red to yellow
ar
(d) Base – Weak; Acid – Strong; End point – Yellow to pinkish red
.le
4. An aqueous solution contains an unknown concentration of Ba 2+ . When 50 mL of a 1 M solution

w
of Na2 SO4 is added, BaSO4 just begins to precipitate. The final volume is 500 mL. The solubility
w
product of BaSO4 is 1×10−10 . What is the original concentration of Ba 2+ ? (2018)

w
(a) 1.0 ×10−10 M

(b) 5 ×10−9 M
(c) 2 ×10−9 M
(d) 1.1×10−9 M
5. The equilibrium constant at 298 K for a reaction, A + B  C + D is 100. If the initial

concentrations of all the four species were 1 M each, then equilibrium concentration of D (in mol
L−1 ) will be (2016)
(a) 0.818
(b) 1.818
(c) 1.182
(d) 0.182

@aakashallen
6. The standard Gibbs energy change at 300 K for the reaction, 2A  B + C is 2494. 2J. At a
1 1
[ A] =
given time, the composition of the reaction mixture is= , [ B ] 2 and [C ] = . The reaction
2 2
proceeds in the
(R = 8.314 JK/mol, e = 2.718) (2015)
(a) forward direction because Q > K C
(b) reverse direction because Q > K C
(c) forward direction because Q < K C
(d) reverse direction because Q < K C
t
ne
1
7. For the reaction, SO2 ( g ) + O2 ( g )  SO3 ( g ) if K p = K C ( RT ) where, the symbols have
x
e.
usual meaning, then the value of x is (assuming ideality)
(a) −1
(b) −
1
iv
at
2
re
1
(c)
2
nc
(d) 1
ar
8. The species present in solution when CO2 is dissolved in water are (2006)
.le
(a) CO2 , H 2CO3 , HCO3− , CO32−

w
(b) H 2CO3 , CO32−

w
(c) HCO3− , CO32−

w
(d) CO2 , H 2CO3
9. N 2 + 3H 2  2 NH 3
Which is correct statement if N 2 is added at equilibrium condition? (2006)
(a) The equilibrium will shift to forward direction because according to IInd law of
thermodynamics, the entropy must increases in the direction of spontaneous reaction
(b) The condition for equilibrium is G ( N 2 ) + 3G ( H 2 ) =
2G ( NH 3 ) where, G is Gibbs free energy
per mole of the gaseous species measured at that partial pressure. The condition of equilibrium is
unaffected by the use of catalyst, which increases the rate of both the forward and backward
reactions to the same extent

@aakashallen
(c) The catalyst will increase the rate of forward reaction by α and that of backward reaction by
β
(d) Catalyst will not alter the rate of either of the reaction
+
10. Ag + + NH 3   Ag ( NH 3 )  ; K1 =
3.5 ×10−3
+ +
 Ag ( NH 3 )  + NH 3   Ag ( NH 3 )2  ; K 2 =
1.7 ×10−3
+
Then the formation constant of  Ag ( NH 3 )2  is (2006)
(a) 6 × 10−6
(b) 6 × 106
(c) 6 × 10−9
t
(d) None of these
ne
e.
11. Consider the following equilibrium in a closed container
N 2O4 ( g )  2 NO2 ( g )
iv
At a fixed temperature, the volume of the reaction container is halved. For this change, which of
at
the following statements hold true regarding the equilibrium constant (K )
p and degree of
re
dissociation (α ) ? (2002)
nc
(a) Neither K p nor α changes

(b) Both K p and α change
ar
(c) K p changes but α does not change

.le
(d) K p does not change but α changes

w
w
12. At constant temperature, the equilibrium constant (K )

p for the decomposition reaction,
w
4x2 p
N 2O4  2 NO2 , is expressed by K p = , where p = pressure, x = extent of decomposition.
(1 − x 2 )
Which one of the following statement is true? (2001)
(a) K p increases with increase of p
(b) K p increases with increase of x
(c) K p increases with decrease of x
(d) K p remains constant with change in p and x
13. When two reactants, A and B are mixed to give products, C and D, the reaction quotient. (Q)
at the initial stages of the reaction (2000)
(a) is zero

@aakashallen
(b) decreases with time

(c) is independent of time
(d) increases with time
14. For the reversible reaction,

N 2 ( g ) + 3H 2  2 NH 3 ( g )
at 500°C , the value of K p is 1.44 ×10−5 when partial pressure is measured in atmosphere. The
corresponding value of K c with concentration in mol/L, is (2000)
1.44 ×10−5
(a)
( 0.082 × 500 )
−2
t
1.44 ×10−5
ne
(b)
(8.314 × 773)
−2
e.
1.44 ×10−5
(c)
( 0.082 × 773)
2
iv
1.44 ×10−5
at
(d)
( 0.082 × 773)
−2
re
nc
15. For the chemical reaction,

3X ( g ) + Y ( g )  X 3Y ( g )
ar
the amount of X 3Y at equilibrium is affected by (1999)

.le
(a) temperature and pressure

(b) temperature only
w
(c) pressure only

w
(d) temperature, pressure and catalyst

w
16. For the reaction,

CO ( g ) + H 2O ( g )  CO2 ( g ) + H 2 ( g ) ,
at a given temperature, the equilibrium amount of CO2 ( g ) can be increased by (1998)
(a) adding a suitable catalyst
(b) adding an inert gas
(c) decreasing the volume of the container
(d) increasing the amount of CO(g)

@aakashallen
17. One mole of N 2O4 ( g ) at 300 K is kept in a closed container udner one atmosphere. It is heated
to 600 K when 20% by mass of N 2O4 ( g ) decomposes to NO2 ( g ) . The resultant pressure is
(1996)
(a) 1.2 atm
(b) 2.4 atm
(c) 2.0 atm
(d) 1.0 atm
18. An example of a reversible reaction is (1985)

(a) Pb ( NO3 )2 ( aq ) + 2 NaI ( aq ) =PbI 2 ( s ) + 2 NaNO3 ( aq )
(b) AgNO3 ( aq ) + HCl ( aq ) = AgCl ( s ) + HNO3 ( aq )
t
ne
(c) 2 Na ( s ) + 2 H 2O (=
l ) 2 NaOH ( aq ) + H 2 ( g )
(d) KNO3 ( aq ) + NaCl ( aq ) =KCl ( aq ) + NaNO3 ( aq )
e.
iv
19. Pure ammonia is placed in a vessel at a temperature where its dissociation constant (a) is
at
appreciable. At equilibrium, (1984)
N 2 + 3H 2  2 NH 3
re
(a) K p does not change significantly with pressure

nc
(b) α does not change with pressure

(c) concentration of NH 3 does not change with pressure
ar
(d) concentration of hydrogen is less than that of nitrogen

.le
20. For the reaction, H 2 ( g ) + I 2 ( g )  2 HI ( g ) the equilibrium constant K p changes with

w
(1981)
w
(a) total pressure

w
(b) catalyst
(c) the amount of H 2 and I 2 present
(d) temperature
21. pK a of a weak acid (HA) and pK b of a weak base (BOH) are 3.2 and 3.4, respectively. The
pH of their salt (AB) solution is (2017)
(a) 7.2
(b) 6.9
(c) 7.0
(d) 1.0

@aakashallen
22. How many litres of water must be added to 1 L of an aqueous solution of HCl with a pH of 1
to create an aqueous solution with pH of 2? (2013)
(a) 0.1 L
(b) 0.9 L
(c) 2.0 L
(d) 9.0 L
23. Solubility product constant ( K sp ) of salts of types MX, MX 2 and M 3 X at temperature ‘T’ are
4.0 ×10−8 ,3.2 ×10−14 and 2.7 ×10−15 , respectively. Solubilities ( mol dm )
−3
of the salts at
temperature ‘T’ are in the order (2008)
(a) MX > MX 2 > M 3 X
t
ne
(b) M 3 X > MX 2 > MX
(c) MX 2 > M 3 X > MX
e.
(d) MX > M 3 X > MX 2
iv
2
at 2
24. 2.5 mL of M weak monoacidic base ( K b = 1×10−12 at 25°C ) is titrated with M HCl in
5 15
re
water at 25°C . The concentration of H + at equivalence point is
nc
(K w 1×10−14 at 25°C )
= (2008)
ar
(a) 3.7 ×10−13 M

(b) 3.2 ×10−7 M
.le
(c) 3.2 ×10−2 M

w
(d) 2.7 ×10−2 M

w
25. CH 3 NH 2 (0.1 mole, K b = 5 ×10−4 ) is added to 0.08 mole of HCl and the solution is diluted to
w
one litre, resulting hydrogen ion concentration is (2005)

−11
(a) 1.6 ×10
(b) 8 ×10−11
(c) 5 ×10−5
(d) 8 ×10−2
26. HX is a weak acid ( K a = 10−5 ) . It forms a salt NaX (0.1 M) on reacting with caustic soda. The
degree of hydrolysis of NaX is (2004)
(a) 0.01%
(b) 0.0001%

@aakashallen
(c) 0.1%
(d) 0.5%
27. A solution which is 10−3 M each in Mn 2+ , Fe 2+ , Zn 2+ and Hg 2+ is treated with 10−16 M

sulphide ion. If K sp of MnS, FeS, ZnS and HgS are 10−15 ,10−23 ,10−20 and 10−54 respectively, which
one will precipitate first? (2003)
(a) FeS
(b) MgS
(c) HgS
(d) ZnS
t
28. Identify the correct order of solubility of Na2 S , CuS and ZnS in equeous medium. (2002)
ne
(a) CuS > ZnS > Na2 S
e.
(b) ZnS > Na2 S > CuS
(c) Na2 S > CuS > ZnS
(d) Na2 S > ZnS > CuS
iv
at
re
29. For a sparingly soluble salt Ap Bq , the relationship of its solubility product ( Ls ) with its
nc
solubility (S) is (2001)

(a) Ls = S p + q . p p . q q
ar
(b) Ls = S p + q . p q . q p
.le
(c) Ls = S pq . p p . q q
w
( p+q)
(d) Ls = S pq . ( p. q )
w
w
30. The pH of 0.1 M solution of the following salts increases in the order (1999)
(a) NaCl < NH 4Cl < NaCN < HCl
(b) HCl < NH 4Cl < NaCl < NaCN
(c) NaCN < NH 4Cl < NaCl < HCl
(d) HCl < NaCl < NaCN < NH 4Cl
31. Which of the following solutions will have pH close to 1.0 ? (1992)
(a) 100 mL of (M/10) HCl + 100 mL of (M/10) NaOH
(b) 55 mL, of 04/10) HCl + 45 mL of (M/10) NaOH
(c) 10 mL of (M/10) HCl + 90 mL of (M/10) NaOH
(d) 75 mL of (M/5) HCl + 25 mL of (M/5) NaOH

@aakashallen
32. Amongst the following hydroxides, the one which has the lowest value of K sp at ordinary
temperature (about 25°C ) is (1990)
(a) Mg ( OH )2
(b) Ca ( OH )2
(c) Ba ( OH )2
(d) Be ( OH )2
33. Which of the following is the strongest acid? (1989)

(a) ClO3 ( OH )
t
(b) ClO2 ( OH )
ne
(c) SO ( OH )2
e.
(d) SO2 ( OH )2
iv
at
34. When equal volumes of the following solutions are mixed, precipitation of
AgCl ( K= 1.8 ×10−10 ) will occur only with (1988)
re
sp
(a) 10−4 M ( Ag + ) and 10−4 M ( Cl − )

nc
(b) 10−5 M ( Ag + ) and 10−5 M ( Cl − )

ar
(c) 10−6 M ( Ag + ) and 10−6 M ( Cl − )

.le
(d) 10−10 M ( Ag + ) and 10−10 M ( Cl − )

w
w
35. The pK a of acetyl salicylic acid (aspirin) is 3.5. The pH of gastric juice in human stomach is
w
about 2-3 and the pH in the small intestine is about 8. Aspirin will be (1988)
(a) unionised in the small intestine and in the stomach
(b) completely ionised in the small intestine and in the stomach
(c) ionised in the stomach and almost unionised in the small intestine
(d) ionised in the small intestine and almost unionised in the stomach
36. The compound that is not a Lewis acid is (1985)

(a) BF3
(b) AlCl3
(c) BeCl2
(d) SnCl4

@aakashallen
37. The conjugate acid of NH 2− is (1985)

(a) NH 3
(b) NH 2OH
(c) NH 4+
(d) N 2 H 4
38. The best indicator for detection of end point in titration of a weak acid and a strong base is
(1985)
(a) methyl orange (3 to 4)
(b) methyl red (5 to 6)
t
ne
(c) bromothymol blue (6 to 7.5)
(d) phenolphthalein (8 to 9.6)
e.
39. A certain weak acid has a dissociation constant of 1.0 ×10−4 . The equilibrium constant for its
reaction with a strong base is
iv (1984)
at
(a) 1.0 ×10−4
re
(b) 1.0 ×10−10
nc
(c) 1.0 ×1010

(d) 1.0 ×1014
ar
40. A certain buffer solution contains equal concentration of X − and HX. The K b for X − is 10−10.
.le
The pH of the buffer is (1984)

w
(a) 4
w
(b) 7
(c) 10
w
(d) 14
41. The precipitate of CaF2 , ( K=

sp 1.7 ×10−10 ) is obtained, when equal volumes of which of the
following are mixed? (1982)
(a) 10−4 M Ca 2+ + 10−4 M F −
(b) 10−2 M Ca 2+ + 10−3 M F −
(c) 10−5 M Ca 2+ + 10−3 M F −
(d) 10−3 M Ca 2+ + 10−5 M F −

@aakashallen
42. An acidic buffer solution can be prepared by mixing the solution of (1981)
(a) acetate and acetic acid
(b) ammonium chloride and ammonium hydroxide
(c) sulphuric acid and sodium sulphate
(d) sodium chloride and sodium hydroxide
43. Of the given anions, the strongest base is (1981)

−
(a) ClO
(b) ClO2−
(c) ClO3−
(d) ClO4−
t
ne
44. At 90°C , pure water has  H 3O +  as 10−6 mol L−1 . What is the value of K w at 90°C ? (1981)
e.
(a) 10−6
iv
(b) 10−12 at
(c) 10−14
(d) 10−8
re
nc
45. The pH of 10−8 M solution of HCl in water is (1981)

(a) 8
ar
(b) −8
.le
(c) between 7 and 8

(d) between 6 and 7
w
w
46. A sample of mixture of A(g), B(g) and C(g) under equilibrium has mean molecular mass equal
to 80. The equilibrium is:
w
A( g )  B ( g ) + C ( g )
If initially 4 mole of ‘A’ gas is present then total number of mole at equilibrium is:
[ M A 100,
= = M B 60,
= M C 40]
(a) 5
(b) 2
(c) 6
(d) 4

@aakashallen
47. 𝐶𝐶𝐶𝐶𝐶𝐶𝑂𝑂3 (𝑠𝑠) ⇌ 𝐶𝐶𝐶𝐶𝐶𝐶(𝑠𝑠) + 𝐶𝐶𝑂𝑂2 (𝑔𝑔)

At equilibrium in the above case, ‘a’ moles of CaCO3 , ‘b’ moles of CaO and ‘c’ moles of 𝐶𝐶𝑂𝑂2 are
found. Then, identify the wrong statement:
(a) Moles of CaCO3 will decrease with the addition of inert gas at constant pressure.
(b) Moles of CaCO3 will remain constant with the increase in volume.
(c) If volume of the vessel is halved, then moles of CaCO3 will increase
(d) Moles of CaO will decrease with the increase in pressure.
48. N 2 + 3H 2  2 NH 3 Starting with one mole of nitrogen and 3 moles of hydrogen, at

equilibrium 50% of each had reacted. If the equilibrium pressure is P. the partial pressure of
t
ne
hydrogen at equilibrium would be
(a) P/2
e.
(b) P/3
(c) P/4
(d) P/6
iv
at
49. For the reaction: CaCO3 ( s )  CaO ( s ) + CO2 ( g ) , K p =
re
1.16 atm at 800°C . If 20g of
CaCO3 were kept in a 10 litre vessel at 800°C , the amount of CaCO3 remained at equilibrium
nc
is:
ar
(a) 34%
(b) 64%
.le
(c) 46%
(d) None
w
w
50. The degree of dissociation of N 2O4 (1) obeying the equilibrium, N 2O4 ( g )  2O2 ( g ) , is
w
approximately related to the pressure at equilibrium by:

(a) α ∝ P
1
(b) α ∝
P
1
(c) α ∝ 2
P
1
(d) α ∝ 4
P
51. In the following reaction, 3 A ( g ) + B ( g )  2C ( g ) + D ( g ) , initial moles of B is double of

A. At equilibrium, moles of A and C are equal. Hence % dissociation of B is:

@aakashallen
(a) 10%
(b) 20%
(c) 40%
(d) 5%
52. The value of K p for the reaction, A ( g ) + 2 B ( g )  C ( g ) is 25 atm −2 at a certain

1 1
temperature. The value of K p for the reaction, C ( g )  A ( g ) + B ( g ) at the same
2 2
temperature would be:
(a) 25 atm −1
1
(b) atm −1
t
25
ne
1
(c) atm
5
e.
(d) 5 atm
iv
at
53. For the equilibrium in a closed vessel PCl5 ( g )  PCl3 ( g ) + Cl2 ( g ) , K p is found to be
re
double of K c . This is attained when:
(a) T = 2 K
nc
(b) T = 12.18 K
(c) T = 24.36 K
ar
(d) T = 27.3 K
.le
54. In the following reaction started only with A8 , 2 A8 ( g )  2 A3 ( g ) + 3 A2 ( g ) + A4 ( g ) mole

w
fraction of A2 is found to 0.36 at a total pressure of 100 atm at equilibrium. The mole fraction of
w
A8 ( g ) at equilibrium is:
w
(a) 0.28
(b) 0.72
(c) 0.18
(d) None of these
55. Which of the following chemical equilibria is favored by increase in temperature?

(a) N 2O4 ⇔ 2 NO2 ∆H = +59 kJ mol−1
(b) N 2 + 3H 2 ⇔ 2 NH 3 ∆H =−22k cal mol −1
(c) 2 SO2 + O2 ⇔ 2 SO3 ∆H =−47 k cal mol −1
(d) both (b) and (c)

@aakashallen
56. If 0.5 mole H 2 is reacted with 0.5 mole I 2 in a ten-litre container at 444°C and at same
temperature value of equilibrium constant K c is 49, the ratio of [ HI ] and [ I 2 ] will be:
(a) 7
1
(b)
7
1
(c)
7
(d) 49
57. 1.50 moles each of hydrogen and iodine were placed in a sealed 10 litre container
t
maintained at 717 K. At equilibrium 1.25 moles each of hydrogen and iodine were left behind.
ne
The equilibrium constant, K c for the reaction. H 2 ( g ) + I 2 ( g )  2 HI ( g ) at 717 K is
e.
(a) 0.4
(b) 0.16
(c) 25
iv
at
(d) 50
re
58. If for a particular reversible reaction,

nc
kC = 57 at 355°C and kC = 69 at 450°C then:

(a) ∆H < 0
ar
(b) ∆H > 0
.le
(c) ∆H = 0
(d) ∆H whose sign can’t be determined
w
w
Kp
59. For which of the following reaction, ratio is maximum?
w
Kc
1
(a) CO ( g ) + O2 ( g ) ↔ CO2 ( g )
2
(b) H 2 ( g ) + I 2 ( g ) ↔ 2 HI ( g )
(c) PCl5 ( g ) ↔ PCl3 ( g ) + Cl2 ( g )
(d) 7 H 2 ( g ) + 2 NO2 ( g ) ↔ 2 NH 3 ( g ) + 4 H 2O ( g )
60. In which reaction will an increase in the volume of the container favor the formation of
products?
(a) C ( s ) + H 2O ( g )  CO ( g ) + H 2 ( g )

@aakashallen
(b) H 2O ( g ) + I 2 ( g )  2 HI ( g )
(c) 4 NH 3 ( g ) + 5O2 ( g )  4 NO ( g ) + 6 H 2O ( I )
(d) 3O2 ( g )  2O3 ( g )
61. In a 1 lit. container following equilibrium is established with equal moles of NO2 ( g ) and
184
N 2O4 ( g ) . N 2O4 ( g )  2 NO2 ( g ) , at equilibrium M avg . = , then ratio of K c and total
3
initial moles is
(a) 3
(b) 3/2
(c) 27/4
t
ne
(d) 6
e.
62. PCl5 is 10% dissociated at 1 atm. What is % dissociation at 4 atm.
iv
PCl5 ( g )  PCl3 ( g ) + Cl2 ( g ) at
(a) 40%
(b) 2.5%
re
(c) 5%
nc
(d) 10%
ar
63. The pressure of iodine gas at a particular temperature is found to be 0.111 atm, whereas
the expected pressure is 0.074 atm. the increased pressure is due to I 2  2 I . Calculate
.le
K p for this equilibrium.

w
(a) 0.074
w
(b) 0.148
(c) 0.05
w
(d) None of these
64. The ratio of the rate of diffusion of a sample of N 2O4 partially dissociated in to NO2 to pure
hydrogen was found to be 1:5. Calculate the degree of dissociation of N 2O4 .
(a) 0.84
(b) 0.54
(c) 0.42
(d) 0.64
65. For the reaction 4 NO2 ( g ) + O2 ( g )  2 N 2O5 ( g ) , which of the following facts holds good?

@aakashallen
(a) K p = K c
(b) K p > K c
(c) K p < K c
(d) K p and K c cannot be correlated unless pressure of the system is provided
66. K p for equilibrium N 2O4  2 NO2 is 0.25 at 15°C If the system is allowed to expand and
N 2 is added at a constant pressure of 1 atm. What will be the degree of dissociation when
partial pressure of N 2 is 0.6 atm.
(a) 0.38
(b) 0.23
t
(c) 0.61
ne
(d) 0.55
e.
67. In an aqeous solution of volume 500 ml when the reaction
iv
2 Ag + ( aq ) + Cu ( s )  Cu 2+ ( aq ) + 2 Ag ( s ) reached equilibrium, the Cu 2+  was ‘a’ M. If 500
at
ml water is further added, at the equilibrium Cu 2+  will be:
re
(a) ' a '/ 2 M
nc
(b) ' a ' M

(c) between ‘a’ and ' a / 2 ' M
ar
(d) less than ' a / 2 '

.le
68. K P for CaCO3 ( s )  CaO ( s ) + CO2 ( g ) is 0.5 at 1000 K. 2 moles of CaO ( s ) and CO2 ( g )
w
each at 0.45 atm introduced in a 16.4 lit. vessel and heated upto 1000 K. The amount of CaCO3 ( s )
w
formed will be
w
(a) 2 mole
(b) 0.01 mole
(c) 1.9 mole
(d) 1 mole
69. For the reaction N 2O4 ( g )  2 NO2 ( g ) ∆H =

57.49 kJ / mole , the vapour density of
equilibrium mixture ……. with increase of temperature.
(a) increases
(b) decreases
(c) remain same
(d) cannot be predicted

@aakashallen
70. 5.1 g of solid NH 4 HS is introduced in a 16.4 lit. vessel and heated upto 500 K. K p for
equilibrium NH 4 HS ( s )  NH 3 ( g ) + H 2 S ( g ) is 0.16. The maximum pressure developed in the
vessel will be:
(a) 0.8 atm
(b) 0.40 atm
(c) 0.5 atm
(d) None of these
71. For the reaction N 2 ( g ) + 3H 2 ( g )  2 NH 3 ( g ) , ∆H =−93.6 kJ mol −1 . The concentration of

H 2 at equilibrium will increase if
t
ne
(a) the temperature is lowered
(b) the volume of the system is decreased
e.
(c) N 2 is added at constant volume
(d) NH 3 is added
iv
at
72. For the reaction 2 NH 3 ( g )  N 2 ( g ) + 3H 2 ( g ) − x kcal , which is correct?
re
(a) degree of dissociation will increase on decreasing temperature.
nc
(b) on decreasing the volume of container degree of dissociation will increase.

(c) K c will decrease on increasing temperature.
ar
(d) on adding inert gas at constant pressure the amount of ammonia will increase.
.le
73. For a reversible reaction K C < K P and ∆H =−100 kJ the reverse reaction is favoured if:
w
(a) Both P and T are reduced

w
(b) P increased and T decreased

(c) Both P and T are increased
w
(d) P decreased and T increased
74. In a two step exothermic reaction

A2 ( g ) + B2 ( g )  3C ( g )  D ( g ) ; ∆H =−ve , steps 1 and 2 are favoured respectively by
(a) High pressure, high temperature & low pressure, low temperature.
(b) Low pressure, low temperature & high pressure, low temperature.
(c) High pressure, low temperature & low pressure, low temperature.
(d) Low pressure, high temperature & high pressure, high temperature.

@aakashallen
75. For the reaction CaCO3 ( s )  CaO ( s ) + CO2 ( g ) the equilibrium amount of CO2 can be
increased by:
(a) Adding a suitable catalyst
(b) Adding more limestone
(c) Increasing volume
(d) Adding inert gas at constant volume
76. Which one of the following changes would result in darkening of the colour
N 2O4 ( g )  2 NO2 ( g ) ∆H =+ve
(a) increasing pressure
(b) increase in temperature
(c) adding inert gas at constant pressure
t
ne
(d) addition of charcol76
e.
77. For the following equilibrium, 2 SO2 ( g ) + O2  2 SO3 ( g ) the total equilibrium pressure is
iv
P1 . If volume of the system is reduced to 1/2 of this initial volume then equilibrium
at
is re-established. The new equilibrium total pressure will be:
(a) 2P1
re
(b) 3P1
nc
(c) 3.5P1
ar
(d) less than 2P1

.le
78. For the reaction: 2 A + B  3C at 298 K , K c = 49

w
A 3L vessel contains 2, 1 and 3 moles of A, B and C respectively.

w
(a) must proceed in forward direction

(b) must proceed in backward direction
w
(c) must be in equilibrium

(d) cannot be predicted
79. In a reaction mixture containing H 2 , N 2 and NH 3 at partial pressure of 2 atm, 1 atm and 3
atm respectively, the value of K p at 725 K is 4.28 ×10−5 atm −2 . In which direction the net
reaction will go?
N 2 ( g ) + 3H 2 ( g )  2 NH 3 ( g )
(a) Forward
(b) Backward
(c) No net reaction
@aakashallen
(d) Direction cannot be predicted
80. In the following reaction:

2 SO2 ( g ) + O2 ( g )  2 SO3 ( g )
the equilibrium is not attained. The rate of forward reaction is greater than that of backward reaction.
Thus, which of the following is the correct relation between K p and Q p ?
(a) K p = Q p
(b) Q p > K p
(c) Q p < K p
(d) K=
p Q=
p 1
t
ne
81. The equilibrium constant K c for the reaction P4 ( g )  2 P2 ( g ) is 1.4 at 400°C . Suppose that
e.
3 moles of P4 ( g ) and 2 moles of P2 ( g ) are mixed in 2 litre container at 400°C . What is the
value of reaction quotient (Q)?
iv
at
3
(a)
re
2
2
nc
(b)
3
ar
(c) 1
(d) None of these
.le
82. For the reaction A ( g ) + 3B ( g )  2C ( g ) at 27°C , 2 moles of A, 4 moles of B and 6 moles

w
of C are present in 2 litre vessel. If K c for the reaction is 1.2, the reaction will proceed in:
w
(a) forward direction

w
(b) backward direction

(c) neither direction
(d) none of these
83. When sulphur (in the form of S8 ) is heated at temperature T, at equilibrium, the pressure of
S8 falls by 30% from 1.0 atm, because S8 ( g ) is partially converted into S 2 ( g ) .
Find the value of K p for this reaction.
(a) 2.96
(b) 6.14
(c) 204.8

@aakashallen
(d) None of these
84. In the presence of excess of anhydrous SrCl2 , the amount of water taken up is governed by
K p = 1012 atm −4 for the following reaction at 273 K
SrCl2 .2 H 2O ( s ) + 4 H 2O ( g )  SrCl2 .6 H 2O ( s )
What is equilibrium vapour pressure (in torr) of water in a closed vessel that contains SrCl2 .2 H 2O ( s ) ?
(a) 0.001 torr
(b) 103 torr
(c) 0.76 torr
(d) 1.31 torr
t
ne
85. At 87°C , the following equilibrium is established.
H 2 ( g ) + S ( s )  H 2 S ( g ) ; Kc =
0.08
e.
If 0.3 mole hydrogen and 2 mole sulphur are heated to 87°C in a 2 L vessel, what will be the
iv
concentration of H 2 S at equilibrium? at
(a) 0.011 M
(b) 0.022 M
re
(c) 0.044 M
nc
(d) 0.08 M
ar
86. 100 mL of 0.1 M NaOH solution is titrated with 100 mL of 0.5 M H 2 SO4 solution. The pH of
.le
the resulting solution is: (For H 2 SO4 , K a1 = 10−2 )

∞, K a2 =
(a) 7
w
(b) 7.2
w
(c) 7.4
w
(d) 6.8
87. Find the pH of 0.1 M NaHCO3 .

Use data ( K1 =
4 ×10−7 , K 2 = 0.6 ) :
4 ×10−11 for H 2CO3 , log 4 =
(a) 3.7
(b) 8.4
(c) 9.6
(d) None of these

@aakashallen
88. If a solution contains 10−6 M each of X − , Y 2− and Z 3− ions, then upon addition of
AgNO3 ( s ) slowly to the above solution with stirring: (Given:
K sp ( AgX ) =
9 ×10−14 , K sp ( Ag 2Y ) =
4.9 ×10−21 , K sp ( Ag3 Z ) =
5.12 ×10−28 )
(a) Ag3 Z will be the first one to precipitate out.
(b) Ag 2Y will be the first one to precipitate out.
(c) AgX will be the first one to precipitate out.
(d) Nothing can be said with certainity.
89. The indicator constant for an acidic indicator, HIn is 5 ×10−6 M . This indicator appears only in
 In −  1
the colour of acidic form when ≤ and it appears only in the colour of basic form when
[ HIn ] 20
t
ne
[ HIn ] ≤ 1
. The pH range of indicator is [Given: log 5 = 0.7]
 In 
−
40
e.
(a) 4.3 – 6.3
iv
(b) 4.0 – 6.6 at
(c) 4.0 – 6.9
(d) 3.7 – 6.6
re
90. Which solution is not a buffer solution?

nc
(a) NaCN (2 mole) + HCl (1 mole) in 5 L

ar
(b) NaCN (1 mole) + HCl (1 mole) in 5 L

(c) NH 3 (2 mole) + HCl (1 mole) in 5 L
.le
(d) CH 3COOH (2 mole) + KOH (1 mole) in 5 L

w
w
 HPO42− 
91. The pH of blood is 7.4. What is the ratio of  − 
in the blood. pK a ( H 2 PO4− ) = 7.1
H PO
w
 2 4
(a) 2:1
(b) 1:2
(c) 3:1
(d) 1:3
92. How much water must be added to 300 mL of a 0.2 M solution of CH 3COOH for the degree
of dissociation of the acid to double ? (Assume K a of acetic acid is of order of 10−5 M )
(a) 900 ml
(b) 300 ml
(c) 600 ml

@aakashallen
(d) 1200 ml
93. 10−2 mole of NaOH was added to 10 litre of water. The pH will change by
(a) 4
(b) 3
(c) 11
(d) 7
94. Given, HF + H 2O 
Ka Kb
→ H 3O + + F − ; F − + H 2O  → HF + OH − . Which relation is correct?
(a) K b = K w
1
(b) K b =
t
Kw
ne
(c) K a × K b =
Kw
e.
Ka
(d) = Kw
Kb
iv
at
95. When salt NH 4Cl is hydrolysed at 25°C , the pH is
re
(a) 7
(b) < 7
nc
(c) > 7
ar
(d) 0
.le
96. A weak acid HA and a weak base BOH are having same value of dissociation constants. If pH
of 0.01 M HA is 4, then pH of 0.01 M BOH will be
w
(a) 3
w
(b) 4
w
(c) 10
(d) 11
97. At 900°C , pK w is 13. At this temperature an aqueous solution with pH = 7 will be

(a) Acid
(b) Basic
(c) Neutral
(d) None of these
98. Which relation is wrong

10−14
(a) 10− pH + 10− pOH =
@aakashallen
1
(b) pH ∝
 H + 
(c) K w ∝ T
= 1.8 ×10−18
(d) dissociation constant of water K
99. pH of an aqueous solution of HCI is 5. If 1 c.c. of this solution is diluted to 1000 times. The pH
will become
(a) 8
(b) 5
(c) 6.9
(d) None
t
ne
100. Dissociation constant of a weak acid is 10−5 . What is the value of equilibrium constant for its
reaction with strong base
e.
(a) 10−5
(b) 10−9
iv
at
(c) 105
re
(d) 109
nc
101. Which will have pH closer to 1:

(a) 100 ml N/10 HCI + 100 ml N/10 NaOH
ar
(b) 55 ml N/10 HCI + 45 ml N/10 NaOH

.le
(c) 10 ml N/10 HCI + 90 ml N/10 NaOH

(d) 75 ml N/5 HCI + 25 ml N/5 NaOH
w
w
102. What is the ∆pH (final – initial) for 1/3 and 2/3 stages of neutralization of 0.1 M CH 3COOH
w
with 0.1 M NaOH:

(a) + 2 log 2
(b) – 2 log 3
(c) 2 log 1/4
(d) 2 log 2/3
103. A weak acid (HA) is titrated with N/100 NaOH. What will be the pH when 50% of titration is
completed. Given K a = 10−4 and concentration of HA = 0.1 M
(a) 4
(b) 8
(c) 6.9

@aakashallen
(d) 10
104. An acid indicator is represented by HI n . ( K a = 10−5 ) . The range of change of colour for the
indicator is
(a) 3 – 5
(b) 4 – 6
(c) 5 – 7
(d) 6 – 8
105. Which will act as a buffer solution

(a) 200 ml N/10 NaOH + 100 ml N/20 HCI
(b) 100 ml 0.1 N NaOH + 100 ml 0.1 N HCI
t
ne
(c) 100 ml 0.1 N NaOH + 50 ml 0.2 N CH 3COOH
(d) 100 ml 0.1 N NaOH + 150 ml 0:1 N HCN
e.
iv
106. 0.1 M NH 4OH and 0.01NH 4OH are taken. Which is a stronger base
at
(a) 0.1NH 4OH
(b) 0.01NH 4OH
re
(c) Both equal

nc
(d) None
ar
107. How many moles of NaOH must be removed from 1 litre of aqueous solution to change its pH
.le
from 12 to 11.
(a) 0.009
w
(b) 0.01
w
(c) 0.02
(d) 0.1
w
108. Solubility of AgBr in water is S1 , in 0.01 M CaBr2 is S 2 . In 0.01 M NaBr is S3 and in 0.05
M AgNO3 is S 4 . The correct order of these solubilities is:
(a) S1 < S 2 > S3 > S 4
(b) S1 < S 2 = S3 > S 4
(c) S 4 < S3 > S 2 > S1
(d) 𝑆𝑆1 > 𝑆𝑆3 > 𝑆𝑆2 > 𝑆𝑆4
109. 0.1 M H 2 S has K1 = 10−6 and K=

2 1.5 ×10−12 . What will be the concentration of S −2 in the
solution.

@aakashallen
(a) ≈ 10−6
(b) ≈ 10−9
(c) ≈ 1.5 ×10−12
(d) 1.2 ×10−13
110. Which has maximum solubility AB, AB2 , AB3 and AB4 if K SP for all the salts are 10−10 :
(a) AB
(b) AB2
(c) AB3
(d) AB4
t
ne
111. Four acids HA, HB, HC and HD form salts with NaOH of pH 7,8,9 and 10 respectively when
each solution was 0.1 M, the strongest acid is:
e.
(a) HA
iv
(b) HB
(c) HC
at
(d) HD
re
112. Three bases XOH, YOH and ZOH has pK b values 2, 3 and 4 respectively the strongest
nc
conjugate acid is:

ar
(a) XOH 2+
.le
(b) YOH 2+
(c) ZOH 2+
w
(d) All same

w
w
113. Four solution of NH 4Cl are taken with concentration 1 M, 0.1 M, 0.01 M and 0.001 M. Their
degree of hydrolysis are h1 , h2 , and h3 , h4 . What is the gradation of degree of hydrolysis?
(a) h1 > h2 > h3 > h4

(b) h=
1 h=
2 h=
3 h4
(c) h4 > h3 > h2 > h1
(d) None of these
114. pH of 3 ×10−3 M solution of H 3 X will be assuming=

α1 1,=
α 2 1/ 3,=
α 3 negligible
(a) 2.40

@aakashallen
(b) 3.0
(c) 3.4771
(d) 4.0
115. Degree of hydrolysis of 0.25 M CH 3COONa is 10% what will be the degree of hydrolysis if
concentration of CH 3COONa is made 0.01 M
(a) 10%
(b) 1%
(c) 50%
(d) 75%
116. The strengths of acids and bases are directly related to their strengths as electrolytes. The
t
ne
electrical conductivity of 0.1 M HCl:
(a) is higher then 0.1 M CH 3COOH
e.
(b) is lower then 0.1 M CH 3COOH
iv
(c) equal to 0.1 M CH 3COOH at
(d) None
re
117. Calculate the pH of resulting solution obtained by mixing 50 mL of 0.6 N HCl and 50 ml of
nc
0.3 N NaOH.
(a) 0.1
ar
(b) 0.8
(c) 2.1
.le
(d) 4
w
118. 50 ml N/10 NaOH solution is mixed with 50 ml N/20 HCl solution. The resulting solution
w
will
w
(1) Turns phenolphthalein solution pink

(2) Turns blue litmus red
(3) Turns methyl orange red
(4)  H +  < OH − 
(a) only (1) is correct
(b) (1) and (2) are correct
(c) (1) and (4) are correct
(d) all are correct
@aakashallen
119. The amount of ( NH 4 )2 SO4 to be added to 500 mL of 0.01 M NH 4OH solution
( pK a for NH 4+ is 9.26 ) prepare a buffer of pH 8.26 is:

(a) 0.05 mole
(b) 0.025 mole
(c) 0.10 mole
(d) 0.005 mole
120. A solution containing 0.2 mole of dichloroacetic acid ( K a = 5 ×10−2 ) and 0.1 mole sodium
dichloroacetate in one litre solution has  H +  :
(a) 0.05 M
t
(b) 0.025 M
ne
(c) 0.10 M
(d) 0.005 M
e.
iv
at
re
nc
ar
.le
w
w
w

@aakashallen
Answer key:
1. (c) 2. (a) 3. (d) 4. (d) 5. (b) 6. (b) 7. (b) 8. (a) 9. (b) 10. (a) 11. (d) 12. (d)
13. (d) 14. (d) 15. (a) 16. (d) 17. (b) 18. (d) 19. (a) 20. (d) 21. (b) 22. (d) 23. (d) 24. (d)
25. (b) 26. (a) 27. (c) 28. (d) 29. (a) 30. (b) 31. (d) 32. (d) 33. (a) 34. (a) 35. (d) 36. (c)
37. (a) 38. (d) 39. (c) 40. (a) 41. (b) 42. (a) 43. (a) 44. (b) 45. (d) 46. (a) 47. (b) 48. (a)
49. (a) 50. (b) 51. (a) 52. (c) 53. (c) 54. (a) 55. (a) 56. (a) 57. (b) 58. (b) 59. (c) 60. (a)
61. (b) 62. (c) 63. (b) 64. (a) 65. (c) 66. (a) 67. (d) 68. (c) 69. (b) 70. (c) 71. (d) 72. (d)
73. (c) 74. (b) 75. (c) 76. (b) 77. (d) 78. (a) 79. (b) 80. (c) 81. (b) 82. (a) 83. (a) 84. (c)
85. (a) 86. (b) 87. (b) 88. (b) 89. (c) 90. (b) 91. (a) 92. (a) 93. (a) 94. (c) 95. (b) 96. (b)
97. (b) 98. (a) 99. (c) 100. (d) 101. (d) 102. (a) 103. (a) 104. (b) 105. (d) 106. (b) 107. (a)
108. (d) 109. (c) 110. (d) 111. (a) 112. (c) 113. (c) 114. (a) 115. (c) 116. (a) 117. (b) 118. (c)
t
ne
119. (b) 120. (a)
e.
“Detail solutions are mentioned in the content library”
iv
at
re
nc
ar
.le
w
w
w

@aakashallen

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• Relation between Kp and Kc

∆n = (c + d) – (a + b), calculation of ∆n involves only gaseous component.

If T2 > T1 . Then K 2 > K1 provided ∆H = + ve (endothermic reaction)

In the above equation, the unit of R and ∆H should be same.

• Relation between equilibrium constant & standard free energy change

Where ∆Go = standard free energy change

R = Universal gas constant.

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If K is very small (K < 10 3)

Reaction Quotient (Q):

d = vapour density of mixture = observed v. d =

sum of stoichiome tric coeff of product

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External Factor Affecting Equilibrium:

∆n > 0 reaction will shift in the forward direction

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[C = , then V = 1/C (volume of solution is which 1 mole is present) is called dilution, so

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1. In pure water [H+] = [OH-] so it is Neutral.

K=a K=b [ H + ][OH =

Note: pK a of H3O+ ions=-1.74

(a) Strong acid solution:

so [H+] = normality of strong acid solution

(b) Strong base solution:

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Number of H+ ions from l - solution = N2V2,

(f) pH of a weak acid{monoprotic) solulion:

The relative value of these constant is, k1 > k2 > k3

(a) weak acid & strong anionic, kw kw 1 1

Hydrolysis of ployvalent anions or cations

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(b) Similarly for H 2 PO4 and HPO4 amphiprotic anions.

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NaOH 100% reaction is indicated 100% reactions is indicated

NaOH + HCl → NaCl + H 2O NaOH + HCl → NaCl + H 2O

is indicated Na2CO3 + 2 HCl → 2 NaCl + H 2O + CO2

NaHCO3 No reaction is indicated NaHCO3 + HCl → NaCl + H 2O + CO2

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If ionic product K I .P > K sp precipitation occurs,

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(b) Base – Weak; Acid – Strong; End point – Colourless to pink

4. An aqueous solution contains an unknown concentration of Ba 2+ . When 50 mL of a 1 M solution

product of BaSO4 is 1×10−10 . What is the original concentration of Ba 2+ ? (2018)

(a) 1.0 ×10−10 M

5. The equilibrium constant at 298 K for a reaction, A + B  C + D is 100. If the initial

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(a) CO2 , H 2CO3 , HCO3− , CO32−

(b) H 2CO3 , CO32−

(c) HCO3− , CO32−

(d) CO2 , H 2CO3

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(a) Neither K p nor α changes

(c) K p changes but α does not change

(d) K p does not change but α changes

12. At constant temperature, the equilibrium constant (K )

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(b) decreases with time

14. For the reversible reaction,

15. For the chemical reaction,

the amount of X 3Y at equilibrium is affected by (1999)

(a) temperature and pressure