Electrochemical

ELECTROCHEMISTRY PHYSICS
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1 Cell 4 EMF of a cell 7 EMF; KC & ∆G
Left side Right side E0cell= E0Cathode-E0Anode 0 0
3 Faraday‛s law
E cell= 0.0591 log KC, log KC=nE cell
Oxidation Reduction Ecell= RPCathode-RPAnode n
0.0591 Product formed
Anode Cathode Ecell= RPCathode+ OPAnode
∆G= -nFEcell m= EM O2 8g 1 mol=5.6L
Negative Positive Ecell= OPAnode- OPCathode
x It 1mol 23g Na+
4
1 mole= 11.2L
96500
H2 1g
Spontaneous Non-spontaneous 2
In cell, Cathode with high
PHYSICS
EM= AM
∆G<0 ∆G>0 1F=96500 C
Representation
2
RP ,Anode with low RP valency Cl2 35.5g 1 mole= 11.2L
2
makes spontaneous reactions 0 0
of cell E cell>0 E cell<0 1F=charge of 1 mole of e- 1mol 9g Al3+
log KC>0 log KC<0 =96500 C 3 Ag+ 108g 1 mol Cu2+ 31.75g= 1/2 mole
5
Zn| Zn2+|| Cu2+| Cu
Nernst equation
}
Ra| Pa|| Rc| Pc KC>1 KC<1 Na+ + e- → Na ⇒ 1F 1F displaces & gives
Mg2+ + 2e- → Mg ⇒ 2F 1 equivalent of
Galvanisation is applying product
Product
at anode
Reactant
at cathode
Ecell= E0Cell- 0.0591 log Product
n Reactant [ [ coating of Zn
Al3+ + 3e- → Al ⇒ 3F
Electrode potential (EMn+/M) For Zn| Zn2+|| Cu2+| Cu
E.P= Reduction Potential (R.P)
= -Oxidation potential (O.P) Ecell= E0Cell- 0.0591 log Zn2+
2+
[ [ 4 Electrolytic conduction
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2 Cu
If R.P=x,then O.P=-x
of weak electrolytes increases with dilution
For Ni| Ni2+|| Ag+| Ag Resistance(R)= r l Unit of R = Ω
1 Electrolytic cell
Representation of Reduction half reaction: ( degree of dissociation increases)
A r = Ωm
[ [
Mn+ + ne- M
- 0.0591 log Ni + 2
2+
E = E0
cell Cell
2 (Ag ) C = Ω-1=S=mho
Standard Reduction Potential(SRP) Conductance(C) = 1
K = Ω-1m-1 or Sm-1 ∞
strong electrolyte
(EOMn+/M) R1| P1|| R2| P2 R
R.P at 1M and 298K. ANODE CATHODE 1Scm-1 = 100 Sm-1
If R2 then Ecell
Conductivity(K) = 1
SRP is calculated by using SHE ,P1
•Anion goes to anode •Cation goes to cathode r
Respresentation of SHE
•+ve electrode •-ve electrode Molar
H+ | H
(1M) | Pt(s)
2 E0SHE=0 Equivalent
•Oxidation
,
(g,1 bar) •Reduction Conductivity Conductivty
6 Application of eq
•A → A++e- •B+1e- → B-
Nernst Equation •A → An++ne- •Bn+ne- → B- =1000 K =1000 K
weak electrolyte
3 Electrochemical eq
M N
series
√c
Electrode Potential K→Scm-1 K→Scm-1
2
∞ order : KCl > NaCl > LiCl
EMn+/M = E0Mn+/M- 0.0591 log 1
n
Product of electrolysis M→mol L-1 N→eq L-1 Conductance
1
Hydrated Radii
[Mn+] →Scm2 mol-1 →Scm2 eq-1
eq
Nernst equation in SHE Deposition order of cation: (order of R.P)
PH Li+ < K+ < Ca2+< Na+ < Mg2+ < Al3+ < Zn2+
1) EH+/H =-0.0591 log
2 2
2
[H+]2
< Fe2+ < Ni2+ < H+ < Cu2+ < Hg2+ < Ag+ < Au3+
Deposition order of anion
1Scm2 mol-1 = 10-4 Sm2mol-1
= xZ
5 Kohlrausch‛s law
If, PH =1 atm
eq
2)
S042- < N03- < OH- < Cl- < Br- < I-
(R.P.)= E
2
=-0.0591 pH N>M > eq λ∞M(AB2) = λ∞M(A2+) + 2 λ∞M(B-)
+
H /H
Note: 1) For conc. H2SO4 3) For CuSO4 with Cu electrode
(O.P.)= EH
2
+ =+0.0591 pH For H2SO4, Z = 2 (2H+) λ∞eq(AB2) = λ∞M(A2+) + λ∞eq(B-)
/H Anode: Anode:
2
H++1e- → 1/2 H2 Cu → Cu2+ + 2e- NaCl, Z = 1 (1Na+)
Concentration Cells Al2(SO4)3, Z = 6 (2Al3+) For Al2(SO4)3
Cathode: Cathode:
2SO42- → S2O82-+2e- Cu2+ + 2e- → Cu
Flourine: F +2e- 2F- +2.87 Zn | Zn
2+
|| Zn
2+
| Zn (peroxo disulphate ion) for SE increases with dilution (interionic attraction λ∞M(Al2(SO4)3)=2 λ∞M(Al3+)+3 λ∞M(SO42-)
(C ) (C )
decreases)
2
1 2
λ∞eq(Al2(SO4)3) = λ∞eq(Al3+)+ λ∞eq(SO42-)
(
( 2) Very dil. NaCl(H O>>NaCl)
cathode.C 2
Ecell = 0.0591 log 2
= ∞
-b√c (Debye-Huckel Onsagar equation) Application
SRP =O.A. anode.C1 Anode:
n H++1e- → 1/2 H2 λ∞M
= ∞ (limiting molar conductivity)
SRP = R.A. NH4OH= λ∞MNH4Cl + λ∞M NaOH - λ∞MNaCl
At √c=0,
C2 C
(
( SO42-
Metals with high SRP = less reactive >1=>log 2 >0 E cell>0 Cathode:
λ∞M CH3COOH = λ∞M CH3COONa+ λ∞MHCl-λ∞MNaCl
Metals with low SRP = highly reactive C 1
C 1
2OH- → 1/2 O2 + H20
+ 2e- Electroplating
λ∞M BaSO4= λ∞MBaCl2 + λ∞M Na2SO4-2λ∞ NaCl
M
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01 02 RATE LAW
03 04 05
Consider a general reaction,
RATE OF A CHEMICAL REACTION FACTORS INFLUENCING aA + bB product
ORDER AND MOLECULARITY PSEUDO ORDER REACTIONS
decrease in conc of reactant OR Increase in conc of reactant
Time taken
RATE OF REACTION Rate = k[A]a [B]b (law of mass action) Consider a general reaction, Consider the reaction
Time taken
Rate = k[A]x [B]y (rate law expression) aA + bB product H+
C12H22O11 + H O C6 H12O6 + C6H12O6
AVERAGE RATE Factors Effect on reaction rate x & y are determined experimentally and may or may not be equal Rate = k[A]x [B]y
to a & b In these reactions, concentration of water
Consider a reaction: A + B C+ D Increase in concentration Increases molecularity = a + b (one of the reactants) is in excess and its
x & y represents the order of reaction with respect to A & B
∆[A] ∆[B] ∆[C] ∆[D] order = x + y concentration remains constant throughout
- ∆t =- ∆t = ∆t = ∆t Increase in temperature Increases the reaction.
Molecularity Order Thus, rate [C12H22011]
INSTANTANEOUS RATE Presence of catalyst Increases RATE CONSTANT Therefore, order= 1
PHYSICS
Consider a reaction: aA + bB cC+ dD Theoretical concept. An experimentally
Larger the value of k, faster is the reaction. determined quantity.
- 1
d[A] 1 d[B] 1 d[C] 1 d[D] The value of k changes only with temperature for given reaction.
a dt =- b dt = c dt = d dt It cannot be zero, fractional, It can be equal to zero
unit of rate constant = (mol)1-n Ln-1 s-1 infinite and imaginary. positive, negative and fractional.
Unit of Rate = mol litre-¹ s-1
Q During the decomposition of H O , 48 g O QWhich of the following will lead to an increase Q The rate constant of a zero-order reactions has Q When the rate of the reaction is equal to the Q For a pseudo first-order reaction, what is the
is formed per minute at a certain point of time. in the rate of the reaction? the unit rate constant, the order of the reaction is unit of the rate of the reaction?
The rate of formation of water at this point is a) Decrease in temperature (a) s -1 (b) mol L-1 s -1 (a) zero order (a) s -1
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b) Decreasing concentration of reactants (b) first order (b) mol L-1s -1

AIMS 2009
(a) 0.75 mol min -1 (b) 1.5 mol min-1
AMU 2010

AMU 2006
(c) L2 mol-2 s -1 (d) L mol-1 s -1
(d) 3.0 mol min-1 c) Addition of catalyst (c) second order (c) mol-1 L s -1
(c) 2.25 mol min-¹
d) Addition of inhibitor (d) third order (d) mol-2 L2 s -1
chemical kinetics
06 07 08 09 10
ELEMENTARY & COMPLEX REACTIONS INTEGRATED RATE EQUATIONS HALF LIFE PERIOD GRAPHICAL REPRESENTATION ARRHENIUS EQUATION
Zero order Zero order 1.Concentration - time graph 2. Rate - concentration graph
Reactions occurring only in one step are called elementary -Ea
b. First order Slope =

log k
t = [A]0
b. First order c. Second order
[A]0- [A] t k = Ae-Ea/RT
a. Zero order a. Zero order 2.303R
reactions while that involving a sequence of elementary FIRST ORDER TRICKS
reactions, are called complex reactions. k= t
1
2
2k
r= k [A] r= k [A]2

Intercept
t75% = 2t
Rate
Ea 1
Conc Conc Rate Rate
In case of complex reactions, the slowest step is called rate First order 1 logk = logA -2.303R
= log A
First order 2 T 1/T
determining step.
t90% = 2.303
time Conc Conc (Conc)2
time
Note Consider the reaction From slow step k = 2.303
t
log [A]0 t = 0.693
1
3. Half life - concentration graph
NOTE
k k
2
2O 3
3O 2
r = k [O] [O3] [A]t a. Zero order b. First order c. Second order For every 10° rise in temperature, rate
Step - 1 Here
[o] [O3] ; From fast step
Second order Second order
t99.9% = 10t 1 becomes double and hence, rate constant
2 t t t
becomes double.
O3 O2 + O (fast) 1 - 1
k = 1t [A] t = 1
1 1 1
2 2 2
[O2] 1
t [A]0 k [A]0
2
Step - 2 r = k [O3]2 [O2]-1 Conc Conc Conc
A reaction with higher value of Ea will
O + O3 2O2 (slow) have smaller value of rate constant.
Q Suppose the reaction: A + 2B AB2 occurs by Q A first order reaction has a specific Q The half-life period of zero order reaction is Q The graph of t versus initial concentration
1
2 Q The slope of Arrhenius plot (In k vs 1T ) of first
the following mechanism: reaction rate of 10-2 sec-1 . How directly proportional to the ___________ 'a' is for order reaction is - 5 x 103 K. The value of Ea
Step 1 : A + B
B AB slow much time will it take for 20 g of the a) Rate constant t 1

of the reaction is [Given: R=8.314 J K-1 mol-1 )

reactant to reduce to 5 g?
2
Step 2 : AB + B AB2 fast b) Initial concentration of reactants

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NEET 2021
AMU 2012
a
(a) -83 kJ mol -1 (b) 41.5 kJ mol -1
Overall A + 2B AB2 (a) 138.6 sec (b) 346.5 sec c) Final concentration of reactants a) First order
(a) k[A] (b) k[B] (c) k[A][B] (d) k[B]2 d) Concentration of products b) Second order (c) 83 kJ mol -1 (d) 166 kJ mol -1
(c) 693.0 sec (d) 238.6 sec c) Zero order
d) Can't predict
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Expressing Concentration of solutions
Types
Mole fraction Normality: Molality: Molarity :
Mass by volume percentage (w/v) Number of gram Number of moles of Number of moles
equivalents of the solute solute per kilogram of solute in 1L solution
dissolved in one of the solvent
Mass percentage (w/w) litre of solution
Parts per million : For trace quantities
Gaseous Liquid Solid No. of moles of solute×1000
Mass of solute No. of moles of component
Gas-Gas → Mixture of O2 and N2 Gas-Liquid → O2 dissolved in water Gas-Solid → O2 in Pd 100 Mass of solvent (in g)
Volume ofsolution Mass of component in solution
100 Total No.of moles of all components
Liquid-Gas → Chloroform with N Liquid-Liquid → Ethanol dissolved in water Liquid-Solid → Amalgam of Hg with Na Total mass of solution
2
No. of gram equivalent of solute×100 No. of moles of solute×100
Solid-Gas → Camphor in N2 Solid-Liquid → Glucose dissolved in water Solid-Solid → Cu dissolved in gold Vo lume percentage (v/v) Volume of solution (in L) Volume of solution (in L)
No. of parts of components × 10 6
PHYSICS
Gram Equivalents of solute
Volume of component Total no. parts of components of solution Mass of solute
100 =
Total volume of solution Equivalent weight
Molecular mass
SOLUTIONS
Equivalent weight =
valency
Colligative properties
Osmotic pressure =CRT Abnormal molecular mass
Kf× W2× 1000
Depression in freezing point Tf =
Molecular mass different from expected value
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M2 x W1
Endothermic ∆ H > 0, Solubility Increases at high temp. Kb× 1000 x W2 Normal molar mass
sol
Elevation of boiling point Tb = Van‛t Hoff factor (i)=
M2 x W1 Abnormal molar mass
Effect of temperature
W2 x M1 Po1 - P1
Relative lowering of vapour pressure =
Exothermic ∆ sol H < 0, Solubility decreases at high temp. (for dilute solutions) M2 x W1 Po1
Solid in liquid
Obey raoult's law
Effect of Pressure Not significant Ideal solution → ΔHmix= ΔVmix=0
eg: n-hexane and n-heptane
Ethyl bromide + Ethyl chloride,
Raoult’s Law
Solubility Chlorobenzene + Bromobenzene, etc.
For any solution, the partial vapour pressure
of each volatile component is directly proportional
to its mole fraction in solution phase
Effect of temperature Increases with decrease in temperature Do not Obey raoult's law
Non-Ideal solution → ΔHmixor ΔVmix≠ 0
Gas in liquid Azeotropes:
The mixtures of liquids which boil at constant
temperature like a pure liquid and possess same composition
of components in liquid as well as vapour phase are called
Effect of Pressure Increases with increase in Pressure constant boiling mixtures or azeotropic mixtures.
Minimum boiling azeotropes:
They are formed by those liquid pairs which show positive Positive Deviation Negative Deviation
deviations from ideal behaviour. eg: ethanol-water mixture.
ΔHmix > 0 ΔHmix < 0
Henry’s Law
Maximum boiling azeotropes: ΔVmix > 0 ΔVmix < 0
PHYSICS
Partial pressure of gas in vapour They are formed by those liquid pairs which show negative
phase is proportional to the mole deviations from ideal behaviour e.g nitric acid-water mixture. eg: Acetone + Ethyl alcohol, eg: Acetone + Aniline,
fraction of gas in the solution. Water + Ethyl alcohol, HCl + H2O, HNO3 + H₂O,
Carbon tetrachloride + Chloroform, H₂SO4 + H2O,
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Chloroform + Ethanol, Acetone + Chloroform,
p =KHχ Acetone + Carbon disulphide, HNO3 + Chloroform,
Acetone + Benzene, etc. Benzene + Chloroform,
Pyridine + Glacial acetic acid, etc.