1|ChemicalEquilibrium

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ChemicalEquilibrium

LawofMassAction:
Therateofachemicalreactionisdirectlyproportionaltoproductofactivemassesofthereactants,raisedto
stoichiometriccoefficients
aA + bB = cC + uB
Rate of foiwaiu ieaction = R
I
= K
I
|A]
a
|B]
b
Rate of backwaiu ieaction = R
b
= K
b
|C]
c
|B]
d

Atequilibrium;R
I
= R
b
K
I
|A]
a
|B]
b
= K
b
|C]
c
|B]
d

WedefineK
c
=
K
I
K
b
=
|C]
c
|D]
d
|A]
a
|B]
b

K
c
(foiwaiu) =
1
K
c
(backward)

Ifthereactantsandproductsaregaseous;
K
p
=
P
c
c
-P
d
d
P
a
a
-P
b
b
,K
p
= K
c
(RT)
n
n - (mass of piouuct) -(mass of ieactant)
Untts uI K
p
and K

:
0nits of K
p
: (Piessuie)
n
= (atm)
n

0nits of K
c
: (Concentiation)
n
= (molLt)
n

Factorsaffectingequilibriumconstant:
K
c
anu K
p
change only with tempeituie.
Ln [
K
2
K
1
=
H
0
R
T
2
-T
1
T
2
T
1
= 2.SuS log
10
= [
K
2
K
1
, K = Ae
-H
0
RT

Equilibriumconstantforreactiontakingplaceinsteps:
e.g.B
2
0
2
+ 2B
+
+2I
-
= I
2
+2B
2
0
(i)B
2
0
2
+ I
-
= 0B
-
+B0I K
1
=
|OH
-
]|HOI]
|H
2
O
2
]|I
-
]

(ii)B
+
+0B
-
= B
2
0 K
2
=
|H
2
O]
|H
+
]|OH
-
]

(iii)B0I +B
+
+ I
-
= I
2
+ B
2
0 K
3
=
|I
2
]|H
2
O]
|HOI]|H
+
]|I
-
]

K
rcactIon
= K
1
K
2
K
3

EquilibriumconstantandstandardfreeEnergy:
u
0
= -2.SuS RTlog 1u K
P

u
0
= -2.SuS RTlog 1u K
C

LeChatelierPrinciple:
Whenasystemunderequilibriumisdisturbedtheequilibriumshiftsinsuchamannersoastonullifythe
disturbance.
(a)Changetheconcentration:
Ifproductsincreased,reactantsobtainedandifreactantsincreased,productsobtained.
(b)Changeinpressure:
Increasesinpressurecausesequilibriumtoshifttowardslesserno.ofgaseousmolesandviceversa.
(c)Changeintemperature:
Itaffectsendoandexothermicreactionsonly.Temperatureincreaseshelpsendothermicwhiletemperature
decreaseshelpsexothermicreaction.
(d)Additionofcatalyst:
Equilibriumremainsunaffected.Itisreachedquickly.
(e)Additionofinsertgas:
Atconstantvolume,ithasnoeffect;Atconstantpressure,equilibriumshiftstowardslargerno.ofmoles.
2|ChemicalEquilibrium

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AcidsandBases:
(1)ArrheniusTheory:
AcidsareB

iondonorsandbasesare0B
_
donors.
(2)LowryBronstedConcepts:
AcidsareB

iondonorsandbasesareB

accepters.Acidsandbasesexistasconjugatepairs.
BCl + B - 0B = B
3
0

+ Cl
_
BCl, Cl
_
conjugate aciu - base paii.
acidbaseacidbase
BN0
3
+ NB
3
= NB
4

+ N0
3
_
NB
3
, NB
4

conjugate aciu -base paii.

acidbaseacidbase
(3)LewisAcidBaseconcept:
Acidsareelectronpairaccepters.Basesareelectronpairdonors.
EquilibriuminAcidsandBases:
Strongacidsdissociatealmostcompletelyandhencethereisnoequilibrium.(alsostrongbases)
WeakAcids:
BA + B - 0B = B
3
0

+ A
_

c - cococo
uissociation constant: K
a
=
|H
3
O

]|A
_
]
|HA]
=
cu
2
1-u

Byastwald,slawofdilution1 - = = _
K
a
c

|B

] = K
a
C = C
WeakBases:
NB
4
0B = NB
4

+ 0B
_

c - cococo
uissociation constant: K
b
=
|NH
4

]|OH
_
]
|NH
4
OH]
=
cu
2
1-u

= _
K
b
c

|0B
_
] = C = K
b
C
SelfIonizationofwater:
B
2
0 = |B
+
]|0B
-
] = B

+ 0B
_

Ionic piouuct = K
w
= |B

]|0B
_
] = 1u
-14

PHandPOH:
PB = -log|B

] ; P0B = -log|0B
_
]
PB + P0B = 14
Relativestrengthofacidsandbasis:
BA
1
= B

+ A
1
_
; BA
2
= B

+ A
2
_

C
1
o
1
C
1
o
1
C
2
o
2
C
2
o
2

Relative stiength =
|H

] Irom HA
1
|H

]Irom HA
2
=
C
1
u
1
C
2
u
2
= _
Ka
1
C
1
Ka
2
C
2

CommonIoneffect:
Duetothepresenceofastrongelectrolyteinsamesolutionhavingacommonion;dissociationofworkelectrolyte
issuppressed.

3|ChemicalEquilibrium

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BufferSolutions:
(1)Acidbuffer:
Saltofaweakacidandstrongbase+weakacid.
CB
3
C00B = CB
3
C00
_
+B

;CB
3
C00Na = CB
3
C00
_
+Na

K
a
=
|CH
3
COO
_
]|H

]
|CH
3
COOH ]
= |B

] = K
a
|CH
3
COOH ]
|CH
3
COO
_
]

pB = pKa +log
|SaIt]
|AcId]
-Benueison
i
sequation
IfK
a
ofacidishigh(ofrange10
2
,10
3
)
pB = pKa +log
|SaIt]+Cu
|AcId]-Cu

(2)Basebuffer:
Saltofaweakbaseandstrongacid+weakbase.
NB
4
0B = NB
4

+ 0B
_
;NB
4
Cl = NB
4

+ Cl
_

K
b
=
|NH
4

]|OH
_
]
|NH
4
OH ]
= |0B
_
] = K
b
|NH
4
OH ]
|NH
4

]

p0B = pK
b
+ log
|SaIt]
|Basc]
-Benueison
i
sequation
IfK
b
ofbaseishigh(ofrange10
2
,10
3
)
p0B = pK
b
+ log
|SaIt]+Cu
|Basc]-Cu

(3)BufferCapacity:
=
d(b)
d pH
,b=molarityofsolutionperliter

(4)Conjugateacidbasepair:
BX = B

+X
_
K
a
=
|H

]|X
_
]
|HX]

X
_
+ B
2
0 = BX + 0B
_
K
b
=
|HX]|OH
_
]
|H
_
]
; pK
a
+ p K
b
= 14

(5)Bufferofasinglesalt:
Saltofaweakbaseandweakacid
CB
3
C00NB
4
= CB
3
C00
_
+NB
4

Solubilityproduct:
A
x
B
y
= xA
y+
+ yB
x-
,K =
|A
y+
]
x
|B
x-
]
j
|A
x
B
y
]

Solubility piouuct = K
sp
= |A
+y
]
x
|B
-x
]
y

Ionic piouuct = |A
+y
]
x
|B
-x
]
y

Saturation,unsaturationandprecipitation:
Ionic piouuct = K
sp
=Satuiateu solution
Ionic piouuct < K
sp
=unsatuiateu solution
Ionic piouuct > K
sp
=Piecipitation
Hydrolysisofsalts:
(1)Saltofastrongbaseandstrongacid:
Itdoesnotundergohydrolysisatall.
(2)Saltofastrongbaseandweakacid:
4|ChemicalEquilibrium

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A
_
+ B
2
0 = BA + 0B
_

c - ch ch ch
K
h
=
ch
2
1-h
=
|OH
_
]|HA]
|A
_
]
=
K
v
K
a
; h = _
K
h
c
= _
K
v
K
a
C

|0B
_
] = ch = K
h
C = _
K
v
K
a
C =p0B = 7 -
1
2
|log C + pK
a
]
(3)Saltofstrongacidandweakbase:
B

+ B
2
0 = B0B + B

c - ch ch ch
K
h
=
ch
2
1-h
=
|H

]|BOH]
|B

]
=
K
v
K
b
; h = _
K
h
c
= _
K
v
K
b
C

|B

] = ch = K
h
C = _
K
v
K
b
C =p0B = 7 -
1
2
|log C + pK
b
]
(4)Saltofweakacidandweakbase:
B

+ A
_
+ B
2
0 = B0B + BA
c - ch c -ch ch ch
K
h
= [
h
1-h

2
=
|BOH]|HA]
|B

]|A
_
]
=
K
v
K
a
K
b
; h = K
h
= _
K
v
K
a
K
b

|B

] = K
a
[
h
1-h
= K
a
h = _
K
v
K
a
K
b
; |0B
_
] = K
b
[
h
1-h
= K
b
h = _
K
v
K
b
K
a

pB = 7 +
1
2
(pK
a
- K
b
) ; p0B = 7 +
1
2
(pK
b
- K
a
)

OstwaldsTheoryofIndicators:
AnindicatorisaweakorganicacidorbasewhichchangescolourwithinacertainpHrange
eg.Phenolphthaleinweakorganicacid
BPh = B

+ ph
_

Colourlesspink
K
In
=
|H

]|ph
_
]
|HPh]
Foraneutralcolour,|ph
_
] = |BPh] pK
In
= pB
|B

] =
K
n
|HPh]
|ph
_
]
pB = pK
In
+ log
|In
-
]
|HIn]

BIn = B

+ In
_

ColourAColourB
Ingeneralunlessmentioned,colorofHIndominateswhen|BIn] 1u|In
_
]andcolourof|In
_
]isobservedwhen
|In
_
] 1u|BIn]
Colourof|BIn] foi pB < PK
In
- 1,Colourof|In
_
] foi pB > PK
In
+1
Theintermediatetransitioncolouroccursfrom
pB |PK
In
-1, PK
In
+ 1] - Range of inuicatoi
ForexactneutralcolourpB = PK
In

WhilstchoosinganindicatorforatitrationtheequivalenceorneutralizationpHmustbelongtorangeofindicator
preferablypHmustbeclosetoPK
In

Phenolphthalein:8.510.5
MethylOrange:34.5