ChE 302 Chemical engineering laboratory - II

Experiment No. 2 Name of the experiment: Group No. 03 (A2)

STUDY OF DIFFUSION

Submitted by: Md. Hasib Al Mahbub

Student Id: 0902045 Level: 3; Term: 1 Section: A2

Date of performance: 30/05/2013 Date of submission: 08/06/2013

Partners Student Id. 0902041 0902042 0902043 0902044

Department of Chemical Engineering. Bangladesh University of engineering and technology, Dhaka.

Summery
The objective of this experiment was to determine the liquid diffusion coefficient of NaCl solution in distilled/de-ionized water. Mass transfer takes place when there is a concentration gradient of the diffusing component. In this experiment, two known concentration of 1M and 4M NaCl solution were used to measure diffusion coefficient by liquid diffusion coefficient apparatus, electrical conductivity values were monitored at different time with the help of a conductivity meter, Two plots of conductivity against time for solution of different concentration gave the slope which is the rate of conductivity change over time and with Ficks first law of diffusivity (using this slope), diffusivity values were obtained. Diffusivity for 1M NaCl solution was 7.4710-3cm2/min and 0.01305 cm2/min for 4M NaCl solution.

Experimental Setup

Diffusion Cell

Diffusion Vessel Capillaries

Water and NaCl Solution

Conductivity Meter

Conductivity Probe Stirrer Bar Magnetic Stirrer

Figure 1. Schematic diagram of a diffusion coefficient apparatus

Observed Data
Volume of water, V = 1.1 L Length of capillaries, x = 0.5 cm Diameter of capillaries, d = 0.1 cm Number of capillaries, N = 97 Table 1: Observed data for determining diffusivity of NaCl solution
No of obs 1M NaCl Time (min) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 0 0.5 1 2 3 4 5 10 15 20 25 30 35 40 EC (S) 1.12 5.32 27.26 36.45 39.73 41.61 42.51 45.88 48.94 51.12 52.64 55.30 57.19 59.06 4 M NaCl Time (min) 0 0.5 1 2 3 4 5 10 15 20 25 30 35 40 EC (S) 2.94 71.99 91.19 117.60 143.60 158.50 172.40 239.60 266.50 283.50 298.70 310.90 320.30 328.50

Given Data and Calculation of CM from Given Data

Table 2: Given data for determining CM value

Observation No. Volume of Water (mL) Volume of 1M NaCl (mL) 0 2.15 500 3 4 4.427 6.427 835 1203 Conductivity (S)

1 2

5.38 408

We know, V1S1 = V2S2 Here, V1 = Volume of the total solution V2 = Volume of the NaCl solution S1 = Concentration of the total solution S2 = Concentration of the NaCl solution Using the equation (1) (a) For observation no. 1 S1 = 0 M (b) For observation no. 2 V1 = 2.15 ml, S1 = 1M, V2 = (500+2.15) = 502.15 ml V1 S1 = V2 S2 2.15 1 = 502.15 S2 S2 = 4.2810-3mol/L
4

(1)

(c) For observation no. 3 V1 = 4.427 ml, S1 = 1M, V2 = (500+4.427) = 504.427ml V1 S1 = V2 S3 4.427 1 = 504.427 S3 S3 = 8.7810-3mol/L (d) For observation no. 4 V1 = 6.427 ml, S1 = 1M, V2 = (500+6.427) = 506.427ml V1 S1 = V2 S4 6.427 1 = 506.427 S4 S4 = 1.26910-2mol/L

S1 = S2 S1 = 4.2810-3mol/L S2 = S3 S2 = 4.510-3mol/L S3 = S4 S3 = 3.9110-3mol/L

Conductivity data from table 2 C1 = 5.38S C2 = 408S C3 = 835S C4 = 1203S C1 = C2 C1 = 402.62S C2 = C3 C2= 427S C3 =C4 C3= 368S

Now, 1 = 1 = 4.28103 = 94070.09 S/(mol/L)

1

402.62

2 = 2 = 4.5103 = 94888.89S/(mol/L)
2

427

3 = 3 = 3.91103 = 94117.65S/(mol/L)
3

368

Therefore, Average, =

1 +2 +3 3

94070.09+94888.89+94117.65 3

= 94358.88 S/(mol/L)

Calculated Data
From Figure 2, Slope of the line of 1M NaCl solution, s1= 2.204 S/min From Figure 3, Slope of the line of 4M NaCl solution, s2= 2.365 S/min

Table 3: Diffusivity calculation for two different NaCl solutions

No. of obs.

Time (min)

1 M NaCl solution

4 M NaCl solution

Conductivity, k S

Slope, s

Diffusivity, D cm2/min

Conductivity, k S 0.77 74.23 87.22 98.86 105.6 109.7

Slope, s S/min

Diffusivity, D cm2/min

S/min 1 2 3 4 5 6 7 8 9 10 11 12 13 14 0 0.5 1 2 3 4 5 10 15 20 25 30 35 40 1.3 25.44 26.92 28.50 30.08 32.31 34.33 49.54 61.92 73.80 81.94 89.91 96.06 102.3 0.9768 7.4710
-3

113.4 123.7 131.9 139.7 145.5 151.4 156.5 161.6

6.8213

0.01305

Graphical Representation
Graph 1: Conductivity vs Time Graph for 1M NaCl Solution
70 y = 0.9768x + 27.004 R = 0.5782 60

50

Conductivity (S)

40

30

20

10

0 0 5 10 15 20 25 30 35 40 45

Time (min)

Figure 2. Graph of Conductivity vs Time Graph for 1M NaCl Solution

Graph 2: Conductivity vs Time Graph for 4M NaCl Solution

400

350

y = 6.8213x + 107.63 R = 0.8117

300

Conductivity (S)

250

200

150

100

50

0 0 5 10 15 20 25 30 35 40 45

Time (min)

Figure 3. Graph of Conductivity vs Time Graph for 4M NaCl Solution

Sample Calculation
Given, Volume of water, V =1.1 L = 1.11000= 1100 cm3 Length of capillaries, x = 0.5 cm Diameter of capillaries, d = 0.1 cm Number of capillaries, N = 97 Conductivity change per unit molar concentration change, CM = 94358.88 S/(mole/L)

For 1M NaCl solution, Slope of the line, s1 = 0.9768 S/min Therefore, D=

4Vx d2 NMCM dk dt

411000.5

3.1416(0.1)2 97194358.88

0.9768 cm2/min

= 7.4710-3 cm2/min = 1.2510-4 cm2/s

For 4M NaCl solution, Slope of the line, s2 = 6.8213 S/min Therefore, D =

4Vx dk

d2 NMCM dt 411000.5 3.1416(0.1)297494358.87

6.8213 cm2/min

= 0.01305 cm2/min = 2.17510-4 cm2/s

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Theoretical Value of Diffusivity for 1M NaCl

The diffusion coefficient or the electrolyte diffusion coefficient can be given as (Cussler, 1984) Do=
2 D1 D2 (z2 1 C1 + z2 C2 ) 2 D1 z2 1 C1 +D2 z2 C2

Or, since z1C1=z2C2, =

|1 |+|2 | |1 ||2 |

(|

1 |1

+ |

2 |2

)-1

Where, D1 and D2 are the molecular diffusion coefficients of the individual ions, C1 and C2 are the ionic concentrations, z1 and z2 are the valences of the ions. When NaCl salt is dissolved in water, the valences of the two identical for the two ions: that is z1 = z2 and D1(Na+) = 1.33410-9 m2s-1 , D2(Cl-) = 2.03210-9 m2s-1 [Table 6.2-1 of Solute diffusion, Physical Method by J. H. Dane and G. C. Topp, Appendix A: Diffusion Co-efficient Table] Do = 2/ (1/D1 + 1/D2) = 1.61110-9 m2s-1 = 1.61110-5cm2/s = 9.66610-4 cm2/min This is the theoretical diffusivity value of 1M NaCl solution.

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Results
The results of this experiment can be tabulated as follows:

Table 4: Table for obtained result

Concentration of NaCl solution mol/L Slope, s S/min Diffusivity (Experimental) D cm2/min 1 0.9768 7.4710-3 Diffusivity (Theoretical) D cm2/s 9.66610-4

6.8213

0.01305

-------

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Discussions
From the formula it is found that if concentration gradient increases, diffusivity value also increases. It happened in the experiment also. Theoretical value of 4M solution was not possible to gain. So, the deviation cannot be shown here numerically. But it is guessed the deviation will be higher than that of for 1M solution .When concentration increases, activity coefficient term must be used in the formula. As 4M solution is highly concentrated than 1M solution, this is one of the possible answer for the deviation. The calculated diffusivity is greater than literature value. The theoretical value of diffusivity for 1M NaCl solution is 1.61110-5 cm2/s. but the experimental result was found to be 1.2510-4 cm2/s. this deviation from theoretical value can be explained as follows 1. Another important thing is- 2 solutions were supplied, they were not prepared by us. Concentration might be not 1 or 4 M that was assumed. 2. The velocity of the water across the capillary tips affects the rate of diffusion, and consequently affects the diffusion coefficient. Different stir speeds will give different results. 3. The experiment was done at ambient temperatures and diffusivity increases with increasing temperature. 4. The theoretical value is for 25oC room temperature, but the room temperature in lab was 30oC. So, it is never possible to get the theoretical value at this temperature. 5. The conductivity meter was not very well handled by us. It stopped for a while during data collection of 4M solution. 6. The value given by conductivity meter was continuously fluctuating. It was not possible to take the accurate reading. 7. Time was maintained by using a stopwatch. As it was manually done, there could be some error also. With the above discrepancies our result was deviated from the theoretical one. And finally our objective of this experiment was completed

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