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Determination of The Partial Molar Volume

This document discusses the determination of partial molar volumes in mixtures. It presents theoretical equations showing that for ideal mixtures, the total volume is additive based on the molar volumes of each component. However, for real mixtures the total volume is not additive. Equations are derived relating the partial molar volume of each component in a mixture to the total molar volume and molar fractions of the components. As an example, equations are shown for a two-component ethanol-water mixture, relating the total molar volume to the molar fraction of water and the individual molar volumes of ethanol and water. An experiment is described measuring the densities of ethanol-water mixtures at different compositions to determine partial molar volumes.

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277 views

Determination of The Partial Molar Volume

This document discusses the determination of partial molar volumes in mixtures. It presents theoretical equations showing that for ideal mixtures, the total volume is additive based on the molar volumes of each component. However, for real mixtures the total volume is not additive. Equations are derived relating the partial molar volume of each component in a mixture to the total molar volume and molar fractions of the components. As an example, equations are shown for a two-component ethanol-water mixture, relating the total molar volume to the molar fraction of water and the individual molar volumes of ethanol and water. An experiment is described measuring the densities of ethanol-water mixtures at different compositions to determine partial molar volumes.

Uploaded by

LoveFreequency
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as DOC, PDF, TXT or read online on Scribd
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Determination of the partial molar volume

Theoretical aspects
The volume of a mixture of ideal gases/liquids is calculated by additivity of the volumes
of the components ( the total volume is equal to the sum of the molar volumes of each
component).
The volume of the mixture, can be calculated using the following formula:
v n i Vi 0
, n i number of moles of component i
i
(Eq.1)
Vi0 molar volume of component i
For real mixtures, the total volume isnt an additive property anymore:
v ni Vi 0

(Eq.2)

No matter if it is additive or nor, any extensive property at constant temperature and


pressure is dependent only on the number of moles. So, the total differentiation of such a
function ( in our case , volume), is given by the relation:
v1
dv P ,T
n1
v i
but :
n i

T , P,n

v i
dn1 ....
ni

Vi

dn i ...
T , P ,n

, Vi the partial molar volume of the compone

T, P, n

in the mixture

(Eq.3)
(Eq.1) becomes:

dvT , P Vi dni

(vT,P ) ni Vi

(Eq.4)

The volume of one mole of the mixture (V) is obtained by dividing (eq.3) at the total
number of moles in the mixture(n):
(V ) P ,T Vi
i

ni
Vi x i
ni
i

, x i the molar fraction of the component i (Eq.5)

The volume of a 2-compnent mixture is:


V x1 V1 x 2 V 2

V ( 1 x 2 ) V1 x 2 V 2

We derive (eq.5) with respect to x2:


dV
V 2 V1
dx 2

(Eq.6)

(Eq.6) is exactly the slope of the curve V=f(x2).From (Eq.5) we get:


V V1 x 2 (V 2 V1 )
and if we replace (V 2 V1 ) with the expression in (Eq.6) , we obtain :
V2 V (1 x 2 )

dV
dx 2

(Eq.7)

Working procedure
A mixture of ethyl alcohol-water, with different compositions( x2: 0.2; 0.5;0.7;0.8;0.9) is
studied. In order to calculate the mass of the alcohol and water , the measured volumes
are multiplied with the densities of the pure components, at the room temperature. By
using a picnometer we determine the densities of the each mixture. The molar volume, V,
is obtained by multiplication between the specific volume of the mixture and the
molecular mass of the mixture, M.

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