TITLE: RAYLEIGH’S DIFFERENTIAL DISTILLATION

AIM: To determine the relative volatility of a wide boiling mixture by differential distillation.

APPARATUS
 Quick-fit distillation kit,
 measuring cylinders,
 thermometer,
 pipette,
 burette,
 beakers,
 wash bottle,
 conical flask.

REAGENTS
 Sulphuric acid,
 distilled water,
 methyl orange indicator,
 0.1M sodium carbonate.

PRINCIPLE
The depletion of the liquid feed mixture in a still pot is given by:
wdx = (y-x) dw
Where y = kx,
k = proportionality constant called the VLE constant. The integration of equation above through
definition of y gives: 6
In w/w0 =- 1/k-1 In x/x0
Where W0 is initial feed amount
x0 is initial composition
w is residue amount
x is distillate amount
k = f (α), α= relative volatility.

PROCEDURE
 0.001 M sodium carbonate was prepared.
 50 ml of distilled water was added, followed by 2.5 ml concentrated sulphuric acid in a
double necked round bottomed flask.
 Carefully assembled the quick-fit full set with the thermometer component in its right place.
 Connected the condenser to the cooling-water tubing and place a measuring cylinder under
the condenser tube outlet.
 Heated up the contents and commenced the distillation.
 Collected the distillate (D) every after five milliliters (5 ml).
 Measured the residue amount (w) in ml by subtracting the distillate (D) from the initial feed
(w0)
 Measured the concentration of x (distillate amount) by titrating it against 0.001M sodium
carbonate
 Continued distilling until about 8-9 measuring cylinders for the distillate were obtained.

EXPERIMENT SETUP

Figure 1 EXPERIMENTAL SET UP

WRITE UP
1) Plot graph of In w/w0 vs. In x/x0 for the acid or base

W =W 0−D .

50=W 0−5 .

Therefore W 0 =¿55

The initial concentration will be calculated from the dilution equation,

M 1 V 1=M 2 V 2.

Where; M1 = molarity of the acid, V1 = volume of the acid, M2 = molarity of the base + acid
solution and V2 = volume of the base + acid solution

24∗2.5
M 2= .
52.5

M 1=¿.1.143M

Therefore X 0=1.143 M

W X
The evaluated values for ln ( ) and ln ( ) are tabulated in the table below.
W0 X0

W X
ln ( ) ln ( )
W0 X0
-0.100 1.05
-0.211 1.15
-0.336 1.27
-0.480 1.41
 -0.647 1.56
-0.847 1.74
-1.099 1.96
-1.435 2.25
-1.946 2.65

Y-Val
0
0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8

-0.5

-1

-1.5

-2

-2.5

2) Plot a graph of In w/w0 vs. In x/x0 for water

 Calculating for the concentration of water:

Assuming the temperature is 250C. Density at 250C is 0.997g/ml

Mass = density x volume

0.997g/ml x 50ml = 49.85g H2O

mass
moles=
relative moleculare mass

49.85
moles= =2.769 mol H2O
18
 2.769 mols ×1000
initial concentration ( x 0 )= =50.34 mole /litre
55 mL

TRIAL ONE

Calculation of the concentration of water after the first distillate:

Density of water at 980C = 0.959g/ml

Mass = 0.959g/mL x 5mL = 4.795g

4.795 g
moles = =0.266 mol
18 g /mol

Number of moles of water remaining in the pot

Moles = 2.769 – 0.266 = 2.503moles

2.503 moles∗1000
X1= =50.06 mol /l
50 ml

TRIAL TWO

Calculation of the concentration of water after the second distillate:

Density of water at 980C = 0.959g/ml

Mass = 0.959g/mL x 5mL = 4.795g

4.795 g
moles= =0.266 mol
18

Number of moles remained in the pot

2.503 – 0.266 moles = 2.237moles

2.237 moles∗1000
X2= =49.7 mol /l
45 ml

TRIAL THREE
Density at 980C = 0.959g/ml

Mass = 0.959g/ml x 5 = 4.795g

4.795
moles= =0.266 Moles.
18

Number of moles remaining in the pot

2.237 – 0.266 moles = 1.971moles

1.971∗1000
X3= =49.3 mol /l
40 ml

TRIAL FOUR

Density at 980C = 0.959g/ml

Mass = 0.959 x 5 = 4.795g

4.795
moles= =0.266 moles.
18

Number of moles remaining in the pot

1.971 – 0.266 = 1.705moles

1,705∗1000
X 4= =48.7 mol /l
35 ml

TRIAL FIVE

Density at 980C = 0.959g/ml

Mass = 0.959g/ml x 5 = 4.795g

4.795
moles= =0.266 Moles
18

Number of moles remaining in the pot

1.439 moles∗1000
X5= =47.97 mol /l
30 ml

TRIAL SIX

Density at 980C = 0.959g/ml

Mass = 0.959g/ml x 5 = 4.795g

4.795
moles= =0.266 Moles.
18

Number of moles remaining in the pot

1.439 – 0.266 = 1.173moles

1.173 moles∗1000
X6= =46.92 mol/l
25 ml

TRIAL SEVEN

Density at 980C = 0.959g/ml

Mass = 0.959g/ml x 5 = 4.795g

4.795
moles= =0.266 Moles
18

Number of moles remaining in the pot

1.173 – 0.266 = 0.907moles

0.907 moles∗1000
X7= =45.35 mol /l
20 ml

TRIAL EIGHT

Density at 980C = 0.959g/ml

4.795
moles= =0.266 Moles.
18

Number of moles remaining in the pot

0.907 – 0.266 = 0.641moles

0.641moles∗1000
X 8= =42.7 mol /l
15 ml

TRIAL NINE

Density at 1050C = 0.0006g/ml

Mass = 0.0006g/ml x 5 = 3 x 10-3

3 x 10−3
moles= =1.67∗10−4 Moles.
18

Number of moles remaining in the pot

0.641– 1.67 * 10−4 moles = 0.6408moles

0.6408∗1000
X 9= =25.632 mol /l
25 ml
 W X
ln ( ) ln ( )
W0 X0
-0.100 -0.006
-0.211 -0.013
-0.336 -0.021
-0.480 -0.033
-0.647 -0.048
-0.847 -0.070
-1.099 -0.104
-1.435 -0.165
-1.946 -0.675

Y-Values
0
0 2 4 6 8 10 12

-0.5

-1

-1.5

-2

-2.5

QUESTIONS
From the graph of 1n W/WO versus 1n X/XO for the acid/base and taking the coordinates;

Y1 = -0.201, Y2 = -0.606

X1 = 1.15, X2 = 1.56

Slope = (Y2 – Y1) / (X2- X1)

m = (-0.606 + 0.201) / (1.56 – 1.15)

m = - 0.988

w −1 x
Therefore, from the equation (1) ln = ln
w0 K−1 x 0

M = -1 / (K – 1)

Thus;

-1 / (K – 1) = - 0.988

1 = 0.988(K-1);

K-1 = 1/0.988= 1.012

K = 1.012 + 1 = 2.012

Expressing k as k=y/x and this can expressed in the relative volatility equation as;

(1−x ) y (1−x )
ᾳ= = k
(1− y) x (1− y)

Solving for the mole fractions y and x;

 Calculating the mole fractions of the H 2 SO4 expected as the more volatile
component in vapor and liquid phase of the first trial:
 2.86∗10−3
Y vapour = n H 2 SO 4/ ntotal = =0.0107
2.86∗10−3 +0.266

57
X liquid = n H 2 SO 4/ ntotal = = 0.958
57+2.503

Therefore the relative volatility will be;

(1−x ) y (1−x )
ᾳ= = k
(1− y) x (1− y)

(1−0.958)
α= 2.012
(1−0.0106)

α =0.085

2) SAFETY FACTORS THAT CAN ENSURE FOR A REAL LIFE PROCESS

 The fully charged fire extinguishers must be in place in case of fire and operating tables
should carefully be cleaned to ensure that the corrosive materials are not left on tables.
 The sulphuric acid is not supposed to come in contact with water as it is exothermic and
lead to an explosion. Therefore, when handling sulphuric acid, water should be kept as
far as possible.
 When handling sulphuric acid, the personnel must be in a full protective equipment kit
(goggles, gloves, work suits or overalls, safety boots and helmet) in that sulphuric acid is
highly corrosive and causes chemical burns upon skin contact.
 The equipment or machinery to be used for reactions involving sulphuric acid must be;
i. acid resistant; this is because sulphuric acid reacts with metals to form
sulphates
 sulphuric acid handling should be done at moderate temperatures because sulphuric acid
is highly reactive at high temperatures