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Topic3160 Volumes; Liquid Mixtures: Binary: Method of Tangents The Method of Tangents is an important technique which is readily illustrated

using the volumetric properties of binary liquid mixtures. The starting point is (as always?) the Gibbs - Duhem Equation which leads to equation (a) for systems at fixed temperature and pressure.

n 1 dV1 (mix ) + n 2 dV2 (mix ) = 0

(a) (b)

Dividing by (n 1 + n 2 ) , x1 dV1 ( mix) + x 2 dV2 ( mix) = 0 The molar volume is given by equation (c). Vm ( mix) = x1 V1 ( mix) + x 2 V2 ( mix)

(c)

Hence (at equilibrium, fixed temperature and pressure) the differential dependence of Vm ( mix) on mole fraction x1 is given by equation (d).
& dV (mix ) # dVm (mix ) = V1 (mix ) + x 1 $ 1 ! dx 1 % dx 1 " & dx # & dV ( mix) # + V2 ( mix) $ 2 ! + x 2 $ 2 ! % dx1 " % dx1 " From the Gibbs-Duhem equation, x1 dV1 ( mix) dV ( mix) + x2 2 =0 dx1 dx1 (e) (d)

[Note the common denominator.] Also x 1 + x 2 = 1 . And so, Therefore,


dx1 = dx 2

(f) (g)

dVm ( mix) = V1 ( mix) V2 ( mix) dx1

Combination of equations (c) and (g) yields the following equation. dV ( mix) # & Vm ( mix) = x1 V1 ( mix) + x 2 $ V1 ( mix) m ! dx1 " % Further, Hence, x1 V1 ( mix) + x 2 V1 ( mix) = V1 ( mix) V1 ( mix) = Vm ( mix) + (1 x1 ) dVm ( mix) dx1 (j) (h) (i)

At a given mole fraction, we determine the molar volume of the mixture Vm ( mix) and its dependence on mole fraction. [dVm ( mix) dx1 ] is the

gradient of the tangent at mole fraction x1 to the curve recording the dependence of Vm ( mix) on x1; hence the name of this method of data analysis. This analysis is relevant because, as commented above, we can
* determine the variables V1 ( !), V2* ( !) and Vm ( mix) . E and their Another approach is based on excess molar volumes Vm

dependence on mole fraction at fixed temperature and pressure. Since And


* * Vm ( id ) = x1 V1 ( !) + x 2 V2 ( !) E Vm = Vm ( mix) Vm ( id )

(k)
(! )

From equations (c), and (k),


E * * Vm = x1 V1 ( mix) V1 ( !) x 2 V2 ( mix) V2 ( !)

(m)

We define excess partial molar volumes;


* V1E ( mix) = V1 ( mix) V1 ( !) and E V2 ( mix) = V2 ( mix) V2* ( !) (n)

Hence the excess molar volume of the mixture is related to two excess partial molar volumes.
E Vm = x 1 V1E ( mix) + x 2 V2E ( mix)

(o)

E on mole We use equation (m) to obtain the differential dependence of Vm

fraction x1.
& dV (mix) # E = [V1 (mix) V1* (!)] + x 1 $ 1 dVm ! % dx 1 " & dV ( mix) # & dx # * + $ 2 ! V2 ( mix) V2 ( !) + x 2 $ 2 ! % dx1 " % dx1 "

(p)

We write the Gibbs - Duhem equation in the form shown in equation (e) together with equation (p). Hence, or,
E E dVm dx1 = V1E V2 E E V2 = V1E dVm dx1

(q) (r) (s)

E E Hence using equation (o), Vm = x1 V1E + x 2 V1E x 2 dVm dx1

Thus,

E E V1E = Vm + (1 x1 ) dVm dx1

(t)

E Equation (t) is the excess form of equation (j). A plot of Vm against x1 E shows a curve passing through ' Vm = 0' at x1 = 0 and x1 = 1.

Other than these two reference points, thermodynamics does not define the
E against x1. Thermodynamics does not define the shape of the plot of Vm

shape of the plot of V1E against x1 other than to require that at x1 = 1, V1E is zero. An interesting feature is the sign and magnitude of V1E in the limit that x1 = 0; i.e. at x2 = 1. The volumetric properties of a binary liquid (homogeneous) mixture is
E against, for example, summarised by a plot of excess molar volume Vm

mole fraction x1. In fact this type of plot is used for many excess molar
E properties including G E m and H m . Here we consider a general excess

molar property X E m . The corresponding excess partial molar property of


E chemical substance 1 is X1 which is related to X E m and the dependence E of X E m on x1 at mole fraction x1, dX m dx1 . E E X1 = XE m + (1 x1 ) dX m dx1

(u)

E requires the gradient dX E Calculation of X1 m dx1 as a function of mole

fraction composition. The way forward involves fitting the dependence of


E XE m on x1 to a general equation and then calculating dX m dx1 using the

derived parameters [1-4].


Footnotes

[1] C. W. Bale and A. D. Pelton, Metallurg. Trans.,1974,5,2323. [2] C. Jambon and R. Philippe, J.Chem.Thermodyn.,1975,7,479. [3] M. J. Blandamer, N. J. Blundell, J. Burgess, H. J. Cowles and I. M. Horn, J. Chem. Soc. Faraday Trans.,1990,86,277. [4] A description of a useful procedure for non-linear least squares analysis is given by W. E. Wentworth, J.Chem.Educ.,1965,42,96.