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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
Faradays frst law:
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
/
.

For a third order reaction k


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