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FOUNDATION/TARGET BATCH
CHEMISTRY
Through most innovating teaching style by:
Shailendra Kumar
Meq. Approach
consult for
Harshit
IIT-JEE
booklet of
Jayati
AIEEE
ELECTROCHEMISTRY
www.shailendrakrchemistry.wordpress.com
SCIENCE
TUTORIALS
Shahid Perwez
and
713
983
Asim Ahmad
Navin Kr.
AIPMT
IONIC EQUILIBRIA
# CELL: 9386594202, 9334217743
Rule (1)
A
B
G1 = 0.2kcal
G2 = 0.4 kcal
A + B+2
A+2 + B Grxn
Grxn = G1 + G2 = (0.2kcal) + (0.4 kcal)
= 0.6 kcal
E = G/nF
Rule (2)
If both half cell reactions are non-spontaneous, then
we convert more non-spontaneous reaction into
spontaneous reaction to gain full cell reaction.
A
A+2 + 2e G1 = +0.2 kcal ....(i)
B
B+2 + 2e G2 = +0.5 kcal ....(ii)
Reaction (i) is less non-spontaneous and reaction (ii) is
more non-spontaneous.
Change : B+2 + 2e
Same :
B
+2
A + 2e
B+2 + A
G2 = 0.5 kcal
G1 = +0.2 kcal
B + A+2 Grxn
4
3
Non-spontaneoity
increases
2
1
G = 0 (Rxn is at equilibrium)
0
1
Spontaneoity
2
increases
3
4
Greater the positive value (+ve) of free energy
greater will be non-spontaneity.
Greater the negative value (ve) greater will be
spontaneity
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Rule (3)
If both half cell reactions are spontaneous then we
conv ert less spontaneous reaction into nonspontaneous reaction.
A
A+2 + 2e G1 = 0.5 kcal (more spontaneous)
B
B+2 + 2e G2 = 0.2 kcal (less spontaneous)
Same :
A
A+2 + 2e
+2
Change : B + 2e
B
A + B+2
G1 = 0.5 kcal
G2 = +0.2 kcal
B + A+2 Grxn
Change: A+2 + 2e
B + A+2
B+2 + 2e
B+2 +A
Ecell
Same : A
A+2 + 2e
+2
Change: B + 2e
B
A + B+2
B + A+2 Ecell
Same : B
B+2 + 2e
+2
Change: A + 2e
A
A + B+2
B + A+2 Ecell
A
B
O .P .
+2
(0.0592 n )log[B ]
+2
A + 2e
*
Rule (10) :
A
A+2 + 2e EO.P. = 0.2 Volt
B+2 + 2e
B ER.P.. = 0.5 Volt
Ecell = ?
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A
B
Rule (7)
Same :
Change :
B+2 + A
Rule (11) :
For following type half cell reaction hybrid reaction
quotients (mixture of Qp and Qc) used in place of Qc or
Qp
H2
2H+ + 2e (no. of electron used = 2)
Q Hybrid =
1/2H2
Q Hybrid =
[H + ]
(PH 2 )1/2
Cl2 + 2e
Q Hybrid =
[H + ]2 mol / litre
(PH 2 ) atm
[Cl ]2
(PCl 2 )
Cl
Cl2 + 1e
Q Hybrid =
(PCl 2 )1/2
[Cl ]
Rule(12) :
Emf is mass or mole independent property (intensive
property), but free energy is mass or mole dependent
property (Extensive property)
H2
1/2H2
2H+ + 2e;
+
H + 1e;
+2
B +A
A +B
Ecell = E1 + E2
A+2 + B
Grxn = G1 + G2
Fe
Fe+3 + 3e oxidation half cell, n=3
Fe+3 + 1e
Fe+2 reduction half cell, n= 1
2Fe+3 + 3I
2Fe+2 +I3 full cell rxn, n=2
Fe+2
Fe+3 + 1e oxidation half cell, n=1
A+3 + B + 1e
E3 E1 + E2
A + B+2
B + A+2
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+2
Rule (14) :
If two half cell (no. of electron same or different)
produces full cell reaction then for simplicity we add
directly emf of half cell not G. Addition of G gives
same result but process is lengthy.
A
A+2 + 2e
E1
+2
B + 2e
B
E2
A | A +2 || B +2 | B
[C ]
[C ]
1
1424
3
2 24
14
3
L .H .S .
R .H .S .
Note :
(a)
(b)
(c)
(d)
(e)
Q=
[ A +2 ][B ]
[ A ][B +2 ]
(f)
(g)
(h)
0.0592
logQ
2
CONCEPT OF SPONTANEITY
For the complete study of reaction knowledge of
thermodynamics and chemical kinetics are essential.
Thermodynamics tell us about spontaneity of
reaction (Reaction is spontaneous or not). Chemical
kinetics tells us about the rate of reaction (Reaction is
fast or slow). Spontaneity of the reaction is determined
by thermodynamic parameter like G, S (universe) and
value of emf (For oxidation, Reduction or Redox
Reaction)
Entropy Change (S)
Entropy is thermodynamic state quantity that is measure
of randomness or disorder of the molecule of the
system.
Explanation of entropy on the basis of probability
left
bulb
no. of molecule
A (1 molecule)
A,B (2 molecules)
A,B,C....(n molecules)
6.023 1023
right
bulb
relative prob. of finding all
molecules in left bulb
PA = = ()1
PAB = PAPB = ()2
PABC...... = ()n
23
23
()6.023 10 = 26.023 10
Example :
Melting of ice at 10C. S universe = +ve
Melting of ice at 0C
S universe = 0
Melting of ice at 10C S universe = ve
For spontaneous process :
Ssystem + Ssurrounding = Suniverse
(+ve or, ve) (+ve or ve)
(always +ve)
G = H T S .................. (1)
=
+ Ssys
T
T
T
T
G
H
G = T Suniverse V .V .I
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System
Suniverse
EMF
Spontaneous
reaction
ve
+ ve
+ ve
Non-spontaneous
reaction
+ve
ve
ve
Reaction is at
equilibrium
THERMODYNAMIC EQUILIBRIA
(a)
G 0
RT
G 0
K = anti ln
RT
( G
/RT
K =e
Equilibrium constant (Kp or Kc) can be
calculated by above equation.
ln K =
0
S reaction
K = anti ln
0
S reaction
K = e ( S reaction /R )
(c)
E =E0
RT
ln Q
nF
E =E0
0.0592
ln Q
At equilibrium, Q = K and E = 0.
REACTION QUOTIENT
W hen reactants and products of a given
chemical reaction are mixed it is useful to know whether
the mixture is at equilibrium, and if not, in which direction
the system will shift to reach equilibrium.
If the concentration of one of the reactants or
product is zero, the system will shift in the direction that
produces the missing component. However, if all the
initial concentrations are non zero, it is more difficult to
determine the direction of the move toward equilibrium.
To determine the shift in such case, we use the reaction
quotient (Q). The reaction quotient is obtained by
applying the law of mass action, using initial
concentrations instead of equilibrium concentration.
Reaction quotient in the term of pressure known
as Qp and reaction quotient in the term of concentration
known as QC .
N2 (g ) + 3H2 (g )
2NH3 (g )
Qc =
(PNH3 )2
[NH3 ]2
=
and
Q
P
[N2 ][H2 ]3
(PN2 )(PH2 )3
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(b)
(a)
(b)
Ans:
[N2]0 = 1 105 M
[N2]0 = 1.5 105 M
-Shailendra Kumar
MAIN OBJECTIVES
1.
CONCEPTOFMILLIEQIVALENT.
wt
eq.wt
wt 1000
No of milliequivalent =
eq.wt
wt 1000
No of meq
N=
=
V(ml)
eq.wt V(ml)
No of equivalent =
No of meq = N V(ml)
wt , No of milli mol = wt 1000
No of mol = mol.wt
mol.wt
No of milli mol = M V(ml)
CONVERSION FACTOR
M V.F (Valence Factor) = N
No of mol V.F = No of eq.
No of milli mol V.F = No of meq.
No of eq = mol.wt
V.F
+
3Y
Milliequivalent X + Y
befor reaction 10
6
Milliequivalent
after reaction
2X
No need of
balanced equation
X2Y3
0 (Suppose)
6
Meq of X Reacted = 6
Meq of Y Reacted = 6
Meq of X2Y3 formed = 6
During reaction equal meq of reactant reacted and equal
meq of product formed.
Species
V.F
K+
1
SO42
2
Al+3
3
Ca+2
2
CaSO4
2
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Ionic Equilibria
New Concepts of
1.
2.
3.
4.
5.
6.
7.
8.
9.
Concept of Milliequivalent.
Auto ionisation of pure water.
PH Calculation of strong acid
and strong base.
PH Calculation of weak acid and
weak base.
PH Calculation of weak acid and
weak base in the present of its salt.
Common Ion effect.
Buffer Solution.
Salt hydrolysis.
Solubility Product Principle
H2SO4
AlCl3
Al2(SO4)3
COOH
2H O
COOH 2
K2SO4 Al2(SO4)3 24H2O
2
3
6
2
8
(100)
(100)
100
100
Meq after
0
0
reaction
(a) Wt of NaOH completely reacted in this reaction,
Hence wt of NaOH reacted is 4 gm.
(b) H2SO4 completely reacted in this reaction, hence wt
of H2SO4 reacted is 4.9 gm.
(c) No of meq of Na2SO4 formed is 100
100
No of milli mol of Na2SO4 =
2
No of milli mol of Na2SO4 = 50
No of mol of Na2SO4 = 50 103
= 5 102 mol
Dilution
means addition of solvent (generally H2O)
During dilution, wt of solute remains constant
Mol.wt of solute
Mol of solute
2.
(a)
H2O
or
H2O + H2O
K ionization =
H3O + OH
[H+] [OH]
[H2O]
3.
Kw = [H+] [OH]
Kw = (x + 102)x
1 1014 = (x + 102)x
After solving quardatic equation value of H+ provided by H2O is very less in comparison to H+ provided by
HCl, Hence H+ provided by H2O is neglected.
Hence [H+] = 102
PH = 2
Value of Kw = 1 1014 at 25 C
Ionisation or Dissociation of H2O is Endothermic
reaction. Hence if temp is increased value of Kw
also increase.
Value of Kw at 25 C is 1 1014 .
Kw is known as ionic product of water.
(b)
PH scale (014) valid for Kw (value equal to
1 1014 )
(c) Q. At certain temp (temp greater than 25 C) Value
of kw is 1 1013 What is its neutral point and what
is its PH scale.
Solution :
PH scale ( 013)
Its neutral point is 6.5
Kw = [H+] [OH]
1 1013 = x.x
x2 = 1 1013
x = 1 106.5 = [H+] = [OH]
Hence PH at neutral point is 6.5
(d)
[H+] [OH] solution is Neutral
[H+] > [OH] solution is Acidic
[H+] < [OH] solution is Basic
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Meq of OH
= Millimol of OH (V.F =1)
Meq of strong acid = Meq of H =Millimol of H
N V(ml)
N V(ml)
M V(ml)
Normality of strong acid=Normality of H+ =Molarity of H+
Conclusion : If we want to calculate PH of strong acid then
PH = log 1.11
300
B+
0
After
dissociation
CC
Kb =
[B+] [OH]
=
[BOH]
OH
C . C
C (1 )
Kb
C
[OH] = C = C
Kb = Kbc
C
[OH] = (Kbc)
POH = log[OH]
= log(Kbc)
(1)
(2)
(3)
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we convert molarity acid into normality of acid, which is directly equal to molarity of H+
2
Calculate PH of 1 102 M H2SO4 .
Molarity of H2SO4 = 1 102 M
Normality of H2SO4 = 2 102 N
Normality of H+
= 2 102
+
Molarity of H = 2 102
PH = log [H+]
PH = log (2 102)
5.
PH CALCULATION OF WEAK ACID AND
WEAK BASE IN THE PRESENCE OF ITS SALT.
Na
100%
O
C1
CH3 CO+
O
O
O
C1
H
B.D
C1
A.D
O
CH3COOH
CH3COO +
CH3 COONa
B.D
C2
A.D
C2 C2
C2
O
C2
Ka =
Ka =
[C1+C2] [C2]
C2 C2
[C1+ C2]
[C2 C2]
[acid]
not 100% correct
Example 2 : If we want to calculate PH of NH4OH (C2) in
the presence of NH4Cl (C1)
10
C1
O
NH4OH
B.D
C2
A.D
C2 C2
C2
C2
O
C1
NH4+
O
C1
+OH
Dissociation of NH4OH is
depressed due to NH4Cl
Kb =
[NH4+][OH]
[NH4OH]
Kb =
[C2 + C1][OH]
[C2 C2]
[OH] = Kb
[C2 + C1][C2]
[C2 C2]
[C2 C2]
[C1 + C2]
[C1+ C2]
[C2 C2]
[C1]
[C2]
[salt]
This equation is
[base]
not 100% correct
O
[CH3CO][H+]
=
[CH3COH]
O
[C1+C2] [H+]
[C2 C2]
100%
+Cl
B.D
A.D
NH4
Calculate PH of
(a) 0.002 N acitic acid having 2.3% dissociation.
(b) 0.002 N NH4OH having 2.3% dissociation.
+
(a) [H ] = 2 103 2.3 = 4.6 105 M
100
PH = 5 log 4.6 = 4.3372
2.3
(b) [OH] = C = 2 102 100
= 4.6 105 M
POH = 4.3372
PH = 9.6627
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NH4Cl
PH = (PKa log c)
[H+] = C = KaC
= Ka
C
Condition 2.
NaOH + CH3COOH
CH3COONa + H2O
Meq.B.R 10
10
0
0
(Suppose)
Meq.A.R 0
0
10
10
If solution contains only salt [CH3COONa] then
PH calculate by salt hydrolysis.
Condition 3.
NaOH + CH3 COOH
Meq.B.R 5
10
CH3COONa + H2O
0
0
Meq.A.R 0
5
5
5
If solution contains weak acid and its salt then PH
is calculated by.
[salt]
[base]
Condition 2.
NH4OH + HCl
NH4Cl + H2O
Meq.B.R 5
10
0
0
Meq.A.R 0
5
5
5
PH is calculated by HCl (strong acid)
Condition 3.
NH4OH + HCl
NH4Cl + H2O
Meq.B.R 5
5
0
0
Meq.A.R 0
0
5
5
PH is calculated by salt hydrolysis (NH4Cl)
Millimol.
2.5
0
2.5
2.5
A.R
Solution after reaction contain strong base (NaOH)
Hence PH determined by NaOH
Meq of NaOH = 2.5
N of NaOH = 2.5 = 2.5 102 M
100
[OH] = 2.5 102
POH = 1.6021
PH = 12.3979
(b)
NaOH + CH3 COOH
CH3COONa + H2O
5
0
0
Meq.B.R 2.5
2.5
2.5
Meq.A.R 0
Solution after reaction contains weak acid and its
salt, Hence PH determined by the equation
[salt]
PH = PKa + log
[acid]
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[salt]
[acid]
PH =PKa + log
11
PH = log Ka + log
[CH3 COONa]
[CH3 COOH]
2.5
[CH3COONa] = 100
= 4.74 + log
PH = 4.74
(c)
NaOH + CH3 COOH
5
Meq.B.R 5
CH3COONa + H2O
0
0
Meq.A.R 0
0
5
5
If solution contains salt after reaction then PH determined by salt hydrolysis. Salt hydrolysis discused latter.
Problem (d), (e) and (f) do yourself.
Hints :
(d) PH determined by buffer equation.
(e) PH determined by strong acid (HCl)
(f) PH determined by salt hydrolysis (NH4Cl)
6 & 7. BUFFER SOLUTION AND COMMON ION
EFFECT BUFFER SOLUTION AND COMMON
Buffer solution: solution which possess reserve acidic nature or alkaline nature or solution which resist change in PH
due to dilution or addition of small quantity of acid or alkali
are known as buffer solution.
Example of acidic Buffer
A weak acid + its salt (CH3COOH + CH3COONa)
Basic Buffer
A weak base + its salt (NH4OH + NH4Cl)
Equation acidic buffer is
[salt]
PH = PKa + log
[acid]
Equation for basic buffer is
[salt]
PH = PKa + log
[acid]
2
Calculate change in PH ( PH ) which 0.01 mol
NaOH added into.
(a) 1.0 litre pure water
(b) 1 litre of 0.10M CH3COOH
(c) 1litre solution 0.10 M CH3COOH and 0.10M CH3COONa
(a)
In pure water, [H+] = [OH] = 107
Hence PH1 = 7
After addition of .01 mol of NaOH
[NaOH] = 0.01 = 0.01
1
[OH] = 1 102
POH = 2, PH2 = 12
PH = PH2 PH1 = 127 = 5
NaOH reacts with acetic acid.
NaOH + CH3 COOH
CH3COONa + H2O
Mol.B.R 0.01
0.10
0
0
Mol.A.R 0
(0.010.01)
0.01
0.01
0.09
Solution contains weak acid and its salt, Hence
(b)
= 4.74 + log
0.10
0.10
PH1 = 4.74
PH after addition of NaOH
CH3COONa + H2O
CH3COOH + NaOH
0.10
0.01
0.10
Mol.B.R
(0.10 + 0.01)
[salt]
PH2 = PKa + log
[acid]
0.11
PH2 = 4.74 + log
0.09
0.11
PH = PH2 PH1 = log
= 0.087
0.09
Conclusion : After addition of NaOH PH is very less in
buffer solution (mixture of weak acid and its salt).
Preparation of Buffer
Mol.A.R
(0.100.01) 0
I.
Acidic Buffer
(a) Mixing weak acid and its salt.
(b) Exess weak acid acid and strong base
CH3COOH + NaOH
CH3COONa + H2O
Meq.B.R 10
5
0
0
0
5
5
Meq.A.R 5
(c) Exess basic salt + HCl
CH3COONa + HCl
NaCl + CH3COOH
Meq.B.R 10
2
0
0
0
8
8
Meq.A.R 8
II.
10
12
PH = PKa 1
In the same manner POH of range of basic buffer
[salt]
POH = PKb + log
[base]
POH = PKb 1
2
A physician or lab technician want to prepare buffer
solution having PH = 5 using CH3COOH and CH3COONa.
What will be ratio of [CH3COONa]
[CH3COOH]
(PKa of CH3COOH is 4.74)
PH = PKa + log [salt]
[acid]
[CH3COONa]
5.0 = 7.74 + log
[CH3COOH]
[CH3COONa]
[CH3COOH] = 0.26
[CH3COONa]
= anti log 0.26 = 1.8
[CH3COOH]
log
Note:
Buffer has maximum capicity when its acid has
its PKa as close as possible to the target PH.
A physician want to prepare buffer solution hav2
ing PH = 5 using weak acid and its salt, which of the following weak acid and its salt would be a good choice.
Acid
Salt
PKa
(a)
H3PO4
H2PO42
2.12
(b)
HCOOH
HCO2
3.74
(c)
CH3COOH
CH3COO
4.75
(d)
H2PO42
HPO42
7.21
Ans = c
SALT HYDROLYSIS
Concept Suppose you want to calculate PH of sodium acetate (basic salt) of certain concentration (c)
O
O
CH3CONa
CH3CO + Na (Any salt is
100%
100%
C
0
0 dissociated)
B.D
0
C
C
A.D
anionic hydroysis taken place.
CH3COO + H2O
CH3COOH + OH
C
0
0
B.R
A.R CC
C
C
CH3COO (Acetate ion) bevaves as weak base
[salt]
[acid] 0.1
[salt]
[acid]
PH = PKa + log
[salt]
[acid]
Basic Buffer
(a) Mixing weak base and its salt
NH4OH + NH4Cl
(b) Exess NH4Cl + HCl
(c) Exess NHaCl + NaOH
PH range of buffer solution
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(c)
[salt]
[acid]
PH2 = 4.74 + log 0.01
0.09
PH2 = 3.78
PH of 0.1 M CH3COOH is
PH1 1/2 (PKa log C)
PH1 = 1/2 (4.74 + 1) = 2.87,
PH = PH2 PH1 = 3.78 2.87
PH = 0.91
PH1 = PKa + log [salt]
[acid]
PH2 = PKa + log
It is not correct.
Conjugate acid of weak base is also weak.
Example : Kb of NH4OH is 1.8 105 (W.B)
Kb of NH4+ is 5.6 1010 (W.A)
NH4OH + H+
NH4+ + H2O
[NH4OH][H+][OH]
[NH4+][OH]
1.0 1014
Kw
=
+ =
1.8 105
Ka(NH4 )
Ka (NH4+) =
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[CH3COOH][OH][H+]
[CH3COO][H+]
Kw
1 1014
Kb(CH3COO) = Ka(CH COOH) =
1.8 105
3
Kb(CH3COO) =
13
Solution :
Kw
(a) Kb (CH3COO) = KH = Ka(CH COOH)
3
1 1014
=
1.8 105
= 5.6 1010
Kb(CH3COO)
=
C
(b) h =
5.6 1010
0.01
= 2.3 104
(c) POH = 1/2 (PKb log c)
= 1/2 (PKb(CH3COO) log c)
= 1/2 (9.25 log 0.01)
= 1/2 (9.25 + 2)
= 5.625
PH = 8.375
2
What is PH of 0.5 M aqueous NaCN solution PKb
of CN = 4.70.
NaCN
Na + CN
CN + H2O
HCN + OH
Kb (CN) =
[HCN] [OH]
[CN]
Kb (OCN)
C
KH
=
C
=
Kw
1014
=
Ka (HOCN)C
3.33 104 0.003
NH4Cl
C
0
NH4+ + H2O
Befor hydrolysis C
After hydrolyCCh
sis
NH4+ + Cl
0
0
C
C
NH4OH + H+
0
0
Ch
Ch
Kw
Kb(NH4OH)
1 1014
Ka(NH4+) =
= 5.6 1010
1.8 105
=
Kw = Kb (X) Ka(Hx)
taking log both side
PKw = PKb + PKa
14 = PKb + PKa
A certain buffer solution contains equal concentration of X and Hx. Kb for X is 1010. Calculate PH of
buffer.
Kb for X = 1010
Kw 1 1014
Kb for Hx = Kb =
= 1 104
1.0 1010
PKa for Hx = 4
[salt]
PH = PKa + log
[acid]
PH = 4
SOLUBILITY PRODUCT PRINCIPLE
14
shailendrakrchemistry.wordpress.com
[NH4OH][H+][OH]
[NH4+][OH]
Ka (NH4+ ) = KH =
100 % (generally)
Minimize
BaSO4(s) + H2O
K=
Ba+2(aq) + SO42(aq)
[Ba+2]eq [SO42]eq
BaSO4(s)
eq denotes equilibrium
Ksp
No necessarily
at equilibrium
Qsp
Q Qc
Qp
Qsp
K Qc
Qp
used in chemical
equilibrium
used in ionic
equilibrium
used in
chemical
equilibrium
Necessarily at
equilibrium.
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After dissociation
at equilibrium
= 1.1 105 M
BaSO4(s)
Ba+2(aq) + SO42(aq)
Before
5
0
0
dissociation 1.1 10 M
NaF
15
H2O + MgF2(s)
S
Na+ + F
Due to common
0.1
100%
reaction
ion
+2
Least soluble
smallest Ksp
S2 = Ksp
S = Ksp
For :
Ag2S
4S3 = Ksp
1
Ksp /3
S= 4
108 S5 = Ksp
1
Ksp /5
S = 108
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