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1

Differential Distillation

Rayleigh Equation

( )
i
i i
dx dL
L y x
=

} }
(1)
Integrating:
1 1
( )
i
o io
x L
i
i i L x
dx dL
L y x
=

} }

1
1
ln
( )
i
io
x
i
o i i x
dx L
L y x
=

}
(2)
Where:

o
L Initial amount of liquid in pot, , moles

1
L Remaining amount of liquid in pot, , moles
dL Amount of liquid vaporized in time du
,
i i
dx dy Change in concentration for time interval du

Solution of the relation depends on the form of the equilibrium relationship: ( )
i i
y f x =

a) When
i i i
y m x =

1 1 1
1
1
ln
( ) ( ) ( 1)
i i i
io io io
x x x
i i i
o i i i i i i i x x x
dx dx dx L
L y x m x x m x
= = =

} } }
1 1
1
ln ln
( 1)
i
o i io
x L
L m x
=

(3)
Rewritten in another form:
1
1
1 1
i
m
i
o io
x L
L x

(
=
(

(4)

b) For
i i i i
y mx c = +


1 1 1
1
ln
( ) ( ) ( 1)
i i i
io io io
x x x
i i i
o i i i i i i i i i x x x
dx dx dx L
L y x m x c x m x c
= = =
+ +
} } }


1 1
( 1) 1
ln ln
( 1) ( 1)
i i i
o i i io i
m x c L
L m m x c
+
=
+
(5)

2

c) When the relative volatility
ij
o is constant and the equilibrium expressed is as:
1 ( 1)
ij i
i
ij i
x
y
x
o
o
=
+


1 1
1 1
1
ln
( )
( )
1 ( 1)
(1 ( 1) ) (1 ( 1) )
( 1 ) ( 1)(1 )
i i
io io
i i
io io
x x
i i
ij i
o i i x x
i
ij i
i
x x
ij i i ij i i
i ij ij i i i ij i x x
L dx dx
x
L y x
x
x
x dx x dx
x x x x x
o
o
o o
o o o
= =


+
+ +
= =
+
} }
} }



1 1
( 1)
( 1)(1 ) ( 1)(1 )
i i
io io
x x
ij i i
i
i ij i i ij i x x
x dx
dx
x x x x
o
o o

= +

} }



1 1
1
( 1) (1 ) (1 )
i i
io io
x x
i i
ij i i i x x
dx dx
x x x o
= +

} }


The integration becomes:

1 1
1 1
1 1 1
ln ln ln
( 1) 1 1
io i io
o ij i io i
x x x L
L x x x o
( | | | |
= +
( | |

\ . \ .



1
1 1
1 1 1
ln ( 1) ln
( 1) 1 1
io i io
ij
ij i io i
x x x
x x x
o
o
( | | | |
= +
( | |

\ . \ .



1
1
1 1
ln ln
( 1) 1
i io
ij
ij io i
x x
x x
o
o
( | |
= +
( |

\ .


And finally:

1 1 1
1 1
ln ln ln
( 1) 1
i i
ij
o ij io io
x x L
L x x
o
o
( | |
=
( |

\ .
(6)





3

d) Graphical integration is applied when the equilibrium data ( , )
i i
x y is given in tabular
form:
For each equilibrium point ( , )
i i
x y the value
1
i i
y x
(
(


is calculated:

1
i i
y x
i i
y x
i
y
i
x
- - - -
- - - -
- - - -

A plot of
1
i i
y x
(
(


versus[ ]
i
x is then made and the area under the curve between
1
[ ]
i
x and
[ ]
io
x gives
1
ln
o
L
L
.