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# 78 chemistry today | December 11

Page 78
some Basic coNcePts iN chemistry
Normality = number of gram equivalents of the
solute/volume of the solution (in litre).
Molarity = number of moles of the solute/volume
of the solution (in litre).
No. of gram equivalents

## Weight of the solute in grams

Equivalent weight of the solute
No. of moles
Wt. of the solute in grams
Mol. wt. of the substance
Molality = number of moles of solute/weight of
solvent (in kg)
Normality equation or Molarity equation
N
1
V
1
= N
2
V
2
...(i)
M
1
V
1
= M
2
V
2
...(ii)
When the solutions of two substances (an acid
and a base or an oxidizing and a reducing
substance) react completely, we apply normality
equation viz.
N
1
V
1
= N
2
V
2

(Solution 1) (Solution 2)
In terms of molarity equation, for the reaction
n
1
A + n
2
B Products, we apply
(M
1
V
1
)/n
1
= (M
2
V
2
)/n
2
(A) (B)
Atomic mass of an element

Mass of one atom of the element
Mass of one atom of C 12
12
Equivalent mass

Mass of element
Volume in mL of hydrogen displaced at NTP
11200
Percentage of element

Mass of element
Molecular Mass
100
atomic structure
E h
hc

## h = Plancks constant = 6.626 10

34
J sec
c = velocity of light = 3 10
8
cm/sec
1 1 1
1
2
2
2

,
]
]
]
R
n n
R = Rydberg constant = 109678 cm
1

m r
nh

2

r
n
Z

2
0 529 .
r = radius of the Bohr orbit of electron
E
Z
n
n

2
2
13 6 . eV

Z
n
2
2
1312 kJ/mol
E
n
= Energy of electron in n
th
orbit
v
Z
n
2 188 10
8
. / sec cm
v = Velocity of electron in particular orbit
P E
kZe
r
K E
kZe
r
T E
k Ze
r
. . , . . , .

2 2
2
1
2
1
2
Heisenbergs uncertainty principle
x p
h

4

Dx = uncertainty in position
Dp = uncertainty in momentum
Orbital angular momentum of an electron
+
h
l l
2
1

( )
Magnetic moment + n n ( ) 2 BM
n = number of unpaired electrons
states of matter
Boyles law equation :
V
P
PV PV P V
1
1 1 2 2
or constant or
Charles law equation :
V T
V
T
V T V T or constant or / = /
1 2 2 1
Gay Lussacs law :
P T
P
T
P
T
P
T
or constant or
1
1
2
2

Avogadros law : V n
Equation of State (Ideal gas) : PV = nRT
Values of R : 0.0821 L-atm K
1
mol
1

= 8.314 10
7
ergs K
1
mol
1

= 8.314 J K
1
mol
1
= 1.987(2) cal K
1
mol
1
Density, d
PM
RT

Page 79
80 chemistry today | December 11
Page 80
For a gas at diferent temperatures and pressures
d T
P
d T
P
1 1
1
2 2
2

## Daltons law of partial pressures :

P = p
1
+ p
2
+ p
3
+ .......
Partial pressure of any component (say A),
p
A
= x
A
. P
where x
A
is mole fraction of A and P is total
pressure.
Grahams law of difusion :
r
r
M
M
d
d
1
2
2
1
2
1
(at constant and ) P T
Average kinetic energy of gas :

KE kT
3
2

(for one molecule) where k
R
N
is known as
Boltzmann constant.
Root mean square velocity :

C RT M
rms
3 /
Most probable velocity :

V RT M
mp
2 /
Average velocity : C RT M
av
8 /
Relationship between velocities :
C C V
rms av mp
: : : / : 3 8 2

Compressibility factor :
Z
PV
nRT
m

## van der Waals equation of state :

P
an
V
V nb nRT +
j
(
,
\
,
(

2
2
( )
Boyles temperature :
T
a
Rb
b

Critical temperature : T
c
= 8a/27Rb
Critical pressure : P
c
= a/27b
2
Critical volume : V
c
= 3b
Relation between critical constants :

PV RT
c c c

3
8
C
P
C
V
= R (for 1 mole of gas).

C
C
P
V
1 66 . (for monoatomic gas),
1.40 (for diatomic gas), 1.30 (for triatomic gas)

1
2
1 2
2 1

n d
n d
, where g
1
= surface tension of water;
g
2
= surface tension of another liquid.
log
.
P
P
H
R T T
v 2
1 1 2
2 303
1 1
j
(
,
\
,
(

j
(
,
\
,
(

DH
v
= Latent heat of vaporisation
P
1
and P
2
are vapour pressures at temperature T
1

and T
2
respectively.
Braggs law, nl = 2dsinq, where n = integer,
q = angle of defection

## Density of latice mater

n M
N a
0
3

n = number of atoms in unit cell, M = atomic mass,
a = edge length of the cubic unit cell
r = radius of atom
For simple cubic, r = a/2
For fcc, r a / 2 2 ; For bcc, r =
3 4 a /
chemical BoNdiNg
Ionic potential
Charge on cation
Size of cation

% of ionic character
= 16(X
A
X
B
) + 3.5 (X
A
X
B
)
2
X
A
and X
B
are electronegativities of atoms A and
B respectively
Dipole moment, m = q d
q = electric charge, d = bond length
% of ionic character

( )
( )
observed
theoretical
100
Bond order

N N
b a
2
where N
b
and N
a
are number of electrons in
bonding and antibonding molecular orbitals.
Bond order
Bond length
Bond strength
1
X V SA E +
1
2
( )
X = number of orbitals involved in hybridisation,
V = valence electrons of central atom, SA = number
of surrounding atoms except oxygen, E = charge
Value of X 2 3 4 5 6 7
Hybridisation sp sp
2
sp
3
sp
3
d sp
3
d
2
sp
3
d
3
chemical thermodyNamics
Mechani cal work done ( w) : w H or
w = JH where J = mechanical equivalent of heat
= 4.184 10
7
ergs = 4.184 joules.
Work done when one calorie of heat is produced
= 4.184 J
Heat absorbed or evolved, DQ = mCDt
where, m = mass of substance, C = specifc heat
and Dt = temperature diference.
According to first law of thermodynamics
DE = q + w
where q is the heat absorbed by the system and w
is the work done on the system.
Sign conventions for DE, q and w :
If work is done on the system, w is positive
If work is done by the system, w is negative
If heat is absorbed by the system, q is positive

## chemistry today | December 11 81

Page 81
If heat is given out by the system, q is negative
If energy is absorbed by the system i.e. internal
energy increases, DE is positive.
If energy is released i.e. internal energy of the
system decreases, DE is negative.
Enthalpy, H = E + PV, Enthalpy change,
DH = DE + PDV.
For 1 mole of a gas,

C
E
T
C
H
T
V
V
P
P

j
(
,
\
,
(

j
(
,
\
,
(
and

C
P
C
V
= PDV = R
Work done in reversible isothermal expansion

2 303
10
1
2
. log nRT
P
P
W
compression
2 303
2
1
. log nRT
P
P
Work done in irreversible isothermal expansion
w = P
ext
(V
2
V
1
)
For reversible adiabatic expansion, PV
g
= constant,
TV
g

1
= constant and TP
(1g)/g
= constant where
g = C
P
/C
V
.
Work done during adiabatic expansion of n moles
of an ideal gas = nC
V
(T
2
T
1
).
q
V
= DE and q
P
= DH,
q
P
= q
V
+ Dn
g
RT or DH = DE + Dn
g
RT
where Dn
g
= n
P
n
R
.
Kirchofs equation is

H H
T T
C
E E
T T
C
T T
P
T T
V
2 1 2 1
2 1 2 1

and .
Efciency of heat engine,

W
q
T T
T
q q
q
2
2 1
2
2 1
2
, where

q
2
= heat absorbed by the system at temperature
T
2
of the source
q
1
= heat rejected by the system at temperature T
1

of the sink, W = net work done.
Entropy change, DS = q
rev
/T.
DS
system
+ DS
surr
0, where sign = refers to a
reversible process (equilibrium) and sign > to an
irreversible process (spontaneous process).
DS
fus
= DH
fus
/T
f
and DS
vap
= DH
vap
/T
b
.
Entropy change of an ideal gas (for 1 mole)
S C
T
T
R
V
V
C
T
T
R
P
P
V P
+ + ln ln ln ln
2
1
2
1
2
1
1
2
At constant temperature (isothermal process)
S R
V
V
R
P
P
ln ln
2
1
1
2

At constant volume (isochoric process)

S C
T
T
C
P
P
V V
ln ln
2
1
2
1
At constant pressure (isobaric process)

S C
T
T
C
V
V
P P
ln ln
2
1
2
1

Gibbs energy, G = H TS
Gibbs energy change, DG = DH TDS.
DG = SG (Products) SG (Reactants).
Sign of DH, DG and DS and prediction of
spontaneity:
DH DS DG Remarks
ve
ve
+ve
+ve
+ve
ve
+ve
ve
ve
ve (at low
temperature)
+ve (at high
temperature)
+ve ( at l ow
temperature)
ve (at high
temperature)
+ve
Spont aneous at al l
temperatures
Spontaneous
Non-spotaneous
Non-spontaneous
Spontaneous
Non-spontaneous at all
temperatures
Clausius-Clapeyron equation :
For Liquid

Vapour equilibrium,
log
.
P
P
H
R
T T
T T
v 2
1
2 1
1 2
2 303

,
]
]
]

where P
1
and P
2
are vapour pressures at
temperatures T
1
and T
2
respectively or P
1
and P
2

are the pressures at which the boiling points are
T
1
and T
2
respectively and DH
v
is latent heat of
vaporisation.
vant Hof reaction isotherm :
DG = DG + RT ln K
p
DG = nFE
cell
; DG = RT ln K
Inversion temperature, T
a
bR
i

2
Heat of the reaction = Sum of bond energies of
reactants sum of bond energies of products.
Thermodynamic efciency of Carnot cycle

W
q
T T
T
2
2 1
2
solutioNs
Henrys law : m = kP
m = Mass of the gas dissolved per unit volume
of a solvent
Raoults law:
Partial pressure in solution P
A
= c
A
P
A

## 82 chemistry today | December 11

Page 82
c
A
= mole fraction of A
P
A
= Vapour pressure of pure constituent
Mole fraction of component A in vapour phase
i e Y
P
P
P
P P
A
A A A
A A B B
. .,
+

Relative lowering in vapour pressure
P P
P
w m
w m W M
o s
o

solute
/
( / ) ( / )
P
o
= Vapour pressure of pure constituent
P
s
= Vapour pressure in solution
c
solute
= mole fraction of solute
Elevation in boiling point
T
K w
W m
b
b

1000
;

K
RT
L
b
b
v

2
1000
w = mass of solute, m = molecular mass of solute
W = mass of solvent, T
b
= boiling point of solvent,
L
v
= Latent heat of vaporisation
Depression in freezing point
T
K w
W m
f
f

1000

;

K
RT
L
f
f
f

2
1000
L
f
= Latent heat of fusion
Osmotic pressure, p = CRT
C
n
V
concentration
vant Hof factor :
i = 1 + (n 1)a (In dissociation)
n = number of particles/molecules
a = degree of dissociation
i
n
+
j
(
,
\
,
(
1
1
1

(In association)
n = number of molecules which are associated
a = degree of association
Relation between osmotic pressure and lowering
of vapour pressure
P P
P
M
dRT
o s
o

M = molecular mass of solvent, d = density
chemical equiliBrium
At state of equilibrium,
rate of forward reaction = rate of backward
reaction
Law of chemical equilibrium for a reaction

aA bB cC dD + +

[ ] [ ]
[ ] [ ]
C D
A B
k
k
K
c d
a b
f
b
c
equilibriumconstant
Q = Concentration quotient
At equilibrium Q = K
c
(i) If Q < K
c
i.e., r
f
> r
b
(ii) If Q > K
c
i.e., r
b
> r
f

Equilibrium constant, K = k
f
/k
b
when k
f
and k
b

are the rate constants or velocity constants for
forward and backward reactions respectively.
Equilibrium constant in terms of pressure

K
p p
p p
P
C
c
D
d
A
a
B
b

Relationship between K
P
and K
C
K
P
= K
C
(RT)
Dn
,
where Dn = n
p
n
r
i.e. no. of moles of gaseous
products no. of moles of gaseous reactants.
Units of equilibrium constant = (mol L
1
)
(c + d) (a + b)

or (atm)
(c + d) (a + b)
.
According to vant Hof equation
log ,
2.303 R
K
K
H T T
T T
P
P
2 1
1 2
( )
( )

j
(
,
\
,
(
2
1

where (K
P
)
1
and (K
P
)
2
are the equilibrium constants
at temperatures T
1
and T
2
respectively and DH is
the average enthalpy change in the temperature
range T
1
to T
2
.
Degree of dissociation of PCl
5
is given by

D d
d
=
M M
M
c o
o
, where
D = theoretical vapour density and
d = vapour density afer dissociation (observed V D.),
M
c
= theoretical (calculated) mol. mass
M
o
= observed mol. mass.
Activation energies of forward and backward
reaction, DE = E
a
(f) E
a
(b)
For exothermic reaction, E
a
(f) < E
a
(b), DE = ve
For endothermic reaction, E
a
(f) > E
a
(b), DE = +ve
Standard free energy change
DG = 2.303RT log K
p
ioNic equiliBrium
According to Ostwalds dilution law for a weak
electrolyte, dissociation constant,
K
C
C K C KV

2
2
1
or /
where a = degree of dissociation, C = concentration
in mol L
1
, V = volume of solution in L containing
1 mole of the electrolyte.
For weak monobasic acids,
K C K V
a a
/
For weak monoacidic bases, K C K V
b b
/
Relative strength of two weak monobasic
acids
Strength of acid H
Strength of acid H
1
2
A
A
K
K
a
a

1
2

where K
a
1
and K
a
2
are the dissociation constants
of acids HA
1
and HA
2
respectively.

## chemistry today | December 11 83

Page 83
Ionic product of water, K
w
= [H
3
O
+
][OH

] = 10
14

at 298 K
[H
+
] or [H
3
O
+
] = 10
pH
pH = log[H
3
O
+
], pOH = log[OH

]
pK
w
= pH + pOH = 14 at 298 K
pK
a
= log K
a
, pK
b
= log K
b
pK
a
+ pK
b
= pK
w
= 14 (at 298 K)
K
a
K
b
= K
w
Solubility product of a sparingly soluble salt
A
x
B
y
is given by
A
x
B
y

xA
y+
+ yB
x
; K
sp
= [A
y+
]
x
[B
x
]
y
Hendersons Equation
(i) For an acidic bufer,
pH p
Salt]
[Acid]
+ K
a
log
[
(ii) For a basic bufer, pOH p
Salt]
[Base]
+ K
b
log
[

For salts of weak acid and strong base :
Hydrolysis constant,

K
K
K
h
w
a

Degree of hydrolysis, h
K
C
K
K C
h w
a
;
pH p p p + + + +
1
2
7
1
2
[ log ] [ log ] K K C K C
a w a

where C is the concentration of solution in
mol L
1
.
For salts of strong acid and weak base :
Hydrolysis constant, K
K
K
h
w
b

Degree of hydrolysis, h
K
C
K
K C
h w
b
;
pH p p p +
1
2
7
1
2
[ log ] [ log ] K K C K C
w b b
For salts of weak acid and weak base:
Hydrolysis constant, K
K
K K
h
w
a b

Degree of hydrolysis, h K
K
K K
h
w
a b

;
pH p p p p p + +
1
2
7
1
2
[ ] [ ] K K K K K
w a b a b
Acid-base indicators
Methyl orange, pH 3.2 4.5 (Pink to yellow)
Methyl red, pH 4.4 6.5 (Red to yellow)
Phenolphthalein, pH 8.3 10.5 (Colourless
to pink)
redox reactioNs & electrochemistry
Equivalent weight of oxidant/reductant

Formula weight
Total change in oxidation number

## According to Ohms law (Resistance)

R
V
I

volt
amperes
ohm) (
Conductance (C) =
1
R
= Ohm
1
or mho or
Siemens (S)
R
l
a

where l = distance between electrodes in cm
a = area of cross-section of electrodes in cm
2
r = specifc resistance
where
l
a
R

## = cell constant (cm

1
)
Specifc conductance,

1
or
1
R
l
a
C cell constant
= ohm
1
cm
1
or S cm
1
Equivalent conductance

eq
eq
V
C

1000 1000
normality
Unit = ohm
1
cm
2
g eq
1
or S cm
2
g eq
1
Molar conductance

m
m
V
C

1000 1000
molarity

Unit = ohm
1
cm
2
mol
1
or S cm
2
mol
1
For a sparingly soluble salt e.g. AgCl, BaSO
4
,
etc.
Solubility (mol L
1
)

1000

m

According to Kohlrauschs law
molar conductance +
m c a
x y
where l
c
and l
a
are molar conductivities of cation
and anion respectively.
Equivalent conductance at infnite dilution

eq
c
c a
+
Degree of dissociation,

m
c
m

## Molar conductance at a given concentration

Molar conductancce at infinite dilution
Molar conductivity at infnite dilution for weak
electrolytes
e.g. L

CH
3
COOH
= L

CH
3
COONa
+ L

HCl
L

NaCl
Weight of the substance liberated at anode
w = Zit = ZQ
Z = electrochemical equivalent
i = current passed for time t seconds
Faradays second law :
wt. of metal
wt. of metal
Eq. wt. of
Eq. wt. of
A
B
A
B

## 84 chemistry today | December 11

Page 84
1 F = 96500 C
E
cell
= E
cathode
E
anode

For the cell : aA + bB xX + yY
E E
n
X Y
A B
C
x y
a b
cell cell
] ]
[ ] [ ]
at
0 0591
25
.
log
[ [
DG = nFE (in standard state)
DG = RT lnK = 2.303RT logK
E E
H H H H +
+
2
+
2
H
/ /
. log
[ ]
0 0591
1

= 0 0.0591(log[H
+
]) = 0.0591 pH
As pH of the solution increases, electrode potential
of hydrogen electrode decreases.
For concentration cell Zn | Zn || Zn | Zn
++ ++
( ) ( ) C C
1 2

E
C
C
cell

j
(
,
\
,
(
0 0591
2
2
1
.
log
For gas concentration cell
Pt (H ) | HCl | Pt(H )
2 2
1
P P
2

;

E
P
P
cell
0 0591
1
2
. log
Relation between free energy and cell potential
Type of reaction DG E Type of cell
Spontaneous ve +ve Galvanic
Non-spontaneous +ve ve Electrolytic
Equilibrium 0 0 Dead batery
chemical kiNetics
For the reaction x + y 2z
rate
dx
dt
dy
dt
dz
dt
1
2
For a reversible reaction at equilibrium

dx
dt
dx
dt
j
(
,
\
,
(

j
(
,
\
,
(
forward backward
Average rate
Change in concentration
Time interval

x
t
For zero order reactions,
k
x
t
t
a
k
;
/ 1 2
2

For reactions of 1
st
order,

k
t
a
a x

2.303
log

where a is the initial concentration of the reactant
and t is the time in which amount x has reacted.
Expression for half-life period for reactions of
1st order
t
k
1 2
0 693
/
.
.
For a second order reaction,
k
t
x
a a x

( )
Half-life period for a second order reaction

t
k a
1 2
1
/
.

t
x
a
a x
a x

1
2
2
2 2

( )
( )

## and half-life period for the third order reaction

t
1/2
= 3/2 ka
2
General expression for half-life period of a reaction
of n
th
order, t
1/2
[A
0
]
1 n
or t
A
n
1 2
1
1
/

,

]
]

0

t
k
n
n
n 1
2 303
1
/
.
log

## Amount of the substance lef afer n half-lives

]
]
A
n
0
2

Arrhenius eqn. for efect of temperature on rate
constant, k Ae
E RT
a

/
where k is rate constant,
pre-exponential factor A is collision frequency,
E
a
is activation energy, T is temperature in K,
R is gas constant.
If k
1
and k
2
are rate constants at temperatures T
1

and T
2
respectively, then
log

k
k
E
R
T T
T T
a 2
1
2 1
1 2
2 303

j
(
,
\
,
(
.
Temperature coefcient
+
k
k
t
t
10
k
t
and k
t

+ 10
= rate constant at temperature t and
t + 10.
( )
( )
/
/
t
t
a
a
n
1 2 1
1 2 2
2
1
1

j
(
,
\
,
(

n = order of reaction
+

1
1 2 1 1 2 2
2 1
log( ) log( )
log log
/ /
t t
a a
(t
1/2
)
1
and (t
1/2
)
2
are half lifes at initial concen-
trations a
1
and a
2
respectively.
n
dc
dt
dc
dt
c c

j
(
,
\
,
(

j
(
,
\
,
(

log log
log log
1 2
1 2
c
1
and c
2
are initial concentrations
surface chemistry
x
m
k P
n

1/
x = mass of gas adsorbed, m = mass of adsorbent,
P = pressure of the gas, k and n are constants
In solution phase

x
m
kC
n

1/
, C = concentration of solution
x
m
aP
bP

+ 1
mm