MT 302

Differential Distillation
To verify the Rayleigh’s equation for a differential distillation in a binary system

In the case of a differential distillation, the vapour at any time is in equilibrium with the liquid from which it rises but changes continuously in the composition. Thus, the mathematical approach used must be differential. Assume that L mol of liquid in the still of composition x mol fraction A and that an amount dD mol of distillate is vaporized, of mol fraction y∗ in equilibrium with the liquid. Material Balance The rate of depletion of liquid is equal to the rate of distillate output. The instantaneous rate of depletion of a component in the liquid is therefore, In - out = accumulation 0 − dD = dL Taking balance on more volatile component, 0 − y∗ dD = d(Lx) 0 − y∗ dD = xdL + Ldx y∗ dL = xdL + Ldx Therefore rearrangement gives,



(3) (4)

dL = L

xF xW


dx −x


This equation can be integrated to get the following form which is called the Rayleigh’s Equation, ln F = W
xF xW


dx −x


MT 302-1

where. 5 can be solved analytically (provided the relationship between y∗ and x is available) or graphically (calculating the area under the curve for the plot of 1/(y∗ − x) vs x. F = D+W (7) F xF = DxD + W xW (8) The integral in eqn. W and xw can be obtained by material balance. MT 302-2 . F = moles of feed of composition xF . W = moles of residual liquid of composition xW .

. . w12 ).Apparatus Figure MT 302. eta2b . Start the flow of water through the condenser.. Moelcular weights of A and B. Fill 3/4th (approx. 5. remove the flask and collect next 8 to 10 drops of the distillate in tagged test-tube and then put another flask for the collection of the distillate. w2 . Start heating at a slow rate. η2t . Prepare a calibration plot of mole fraction (x) vs.η12t ). 4. The mixture is weighed (w) before charging in the distillation flask. When the mixture starts boiling. After approximately 30 ml of the distillate has been collected. Observations and Calculations Data from the literature 1. collect the distillate in a weighed 50 ml flask.. η12b ). This procedure should be repeated for collecting 8 distillate samples. Measure the RI of the bulk from each of the flasks (eta1b . Vapour liquid equilibrium data for A and B at atmospheric pressure... 3. Refractive indices of A and B.. 2.0.1: Schematic of the setup Procedure 1. of tagged stoppered conical flasks. Densities of A and B. 300 ml) volume of the distillation flask with a mixture of A and B of known composition (xF )... 4. Weigh the samples collected in the conical flasks (w1 . 6. refractive index (h) of pure components A and B.. MT 302-3 . 3. Measure the refractive indices (RI) of the samples collected in the test-tubes (η1t . Weigh 8 nos. 2.

Calculate x (liquid phase composition in equilibrium with y∗ ) using Raoult’s law. RI S. 3.4 0. Calculate W (amount of residue still left in the flask) and xW (composition of residue) using Eqn. 5.7 0. MT 302-4 . Calculate y∗ (vapor phase composition) for each sample (from Refractive index of 8 drops collected. 2.0 RI Calculations 1.8 0.2 0.5 0.N. Calculate D (amount of distillate) (from weighed 30 ml sample) and xD (distillate composition) (from refractive index of 30 ml sample) for each sample. 1 2 3 4 5 6 7 8 9 10 11 Mole fraction of A 0 0. 7 and 8 for each fraction.3 0.1 0.) 4. Complete the following Table.6 0.9 1.Calibration data for mole fraction vs.

1 2 3 4 5 6 7 8 F xF D xD W xW y∗ x ln(F/W)i 1/(y∗ − x) 6. 9.. 6.S. Now verify Eqn.N. + ln(F/W)8 7. 8. Plot 1/(y∗ − x) vs x and measure the area under the curve. Calculate ln(F/W) = ln(F/W)1 + ln(F/W)2 + . Calculate % Error = ln(F/W) − xF xw dx/(y∗ − x) × 100 ln(F/W) MT 302-5 ..