PRACTICES MANUAL _ediceyay. a= “Unit ref.: QDTLIQDTLE "Date: March 2009 Pg: 9/27 Other very usefull way to express the firs Fick's Law is: Ki =x,(h,+H,)-cDa¥e, 3) 7.2.2, Liquids diffusiv’ ‘The theory of diffusion in liquids is little developed and the experimental data are less abundant than for gases. The liquids diffusivities are usually of 4 to 5 orders of lower magnitude to those of gases at the atmospheric pressure. The diffusion in liquids takes place due to the movement of the molecules at random. But the average distance travelled between the collisions is lower than the molecular diameter, in comparison with the situation of gases, where the average free travel has higher magnitude order than the molecule size. The diffusivities for liquid solutions may be calculated approximately from the equation: = pM OT D, = 74x10 - ww? Where D, = Diffusivity, em?/s T= Absolute temperature, K = Viscosity of the solution, cP V4 = Molar volume of the solute as a liquid in its normal temperature when it comes to boil, cm*/mol-g Wy = Parameter of association for the solvent Ms = Molecular weight of the solventPRACTICES MANUAL Pg: 10/27 fef.: QDTLIQDTLC Date: March 2009 cdi) Example 21.3. Let’s estimate the diffusivity of benzene in toluene and of toluene in benzene at 110°C. The physical properties are: M Te°C V, at Temp cm’/mol cP Benzene 781 COSCON Ot Toluene 92,13 110,6 118,3 0,26 SOLUTION: The Equation (21.23) will be used for benzene in toluene 4x10™* (92,13)! 7383 = =*> = 6,74 x 10% em’/s 0,16(96,5)' The recommended values of y,, are 2,6 for water, 1,9 for methanol, 1,5 for ethanol and 1,0 for benzene, heptano, ether and other solvents that are not associated. They are only valid for low concentrations and are applicable to electrolytes. For watery solutions with low concentration in electrolytes, an easier equation can be used: 3,26x10* Dy= ye Where fg = Water viscosity V, = Molar volume of the solute at its boiling normal temperature, cm*/ mol-g Notice that contrary to the case of binary mixing, the diffusion coefficient for a diluted solution of A in B is not the same than the one corresponding to a diluted solution of B in A, since p, Mg and Vq will be different when the solute and the solvent are swapped. For medium concentrations, sometimes the user can obtain anPRACTICES MANUAL QDTLIQDTLC | 2009 Pg: 11/27 approximated value of D through the interpolation between the values of the solutions in liquids, but this method leads to big mistakes for the case of not ideal solutions. 7.2.3 Conductivity To know the diffusivity of the solute in the solvent, there is a possibility to resort to indirect steps, that is to say, to calculate the diffusivity from another known ~ variable. In this case, since the used solute is a salt (NaCI for example), the user will resort to measure the conductivity. Afterwards, from these data, the diffusivity can be determined. The conductivity is the capacity of a solution to conduct the electric. It can also be defined as a measure of the total ionic concentration that a solution has got. 7.2.3.1 Conductivity measure When the user knows the nature of the involved ion, it can be used to determine the concentration of them. A full system to measure the conductivity is made up of: Y A conductivity cell. vA temperature probe. yA measure instrument. The conductimeter measures the electric conductivity of the ions in a solution. For this, it applies an electric field of the solution. To avoid changes in the substances, effects of layer on the electrodes, etc., an alternating current is applied.PRACTICES MANUAL a edi Unit refi: QDTLIQDTLC Date: March 2009 Pg: 42/27 The usual measure units are S/cm, Other alternative ways to express the conductivity of a solution are the Salinity and the Total Dissolved Solids (TDS). 7.2.3.2 The temperature effect The conductivity of a solution is highly dependent of the temperature. This cone has the double effect on the electrolytes: it has an influence on their solution and on their ionic mobility. ‘The conductivity of a solution increases with the temperature. This increase is expressed normally in %/°C, and it is called Temperature Coefficient (TC). In general, the watery solutions own a TC near 2%/°C. The temperature compensation consists in calculating, from the C, the conductivity value that should have a sample at a so-called Reference Temperature, usually 25°C.7 PRACTICES MANUAL - edioe Unit ref: QDTLIQDTLE —_—_—_—Date: March 2009 Pg: 13/27 7.3 PRACTICES ACCOUNT 7.3.1 Warnings, main instructions and precautions Follow security instructions at any moment. © Organic solvents solutions, such as acetone, ethanol, etc., must not be used, due to the fact that the receptacle of the solution and the diffusion cell as well are made of methacrylate 7.3.2. PRACTICE 0. Account of concentration and conductivity. 7.3.2.1 Objective To find the ratio between the concentration of a saline solution and the conductivity. 7.3.2.2 Necessary elements e Unit QDTL of Edibon Sodium chloride Distilled water A precision balance 7.3.2.3 Practice development In this practice, a graph is going to be drawn, which will give the direct ratio between conductivity and the saline concentration. This table will be very useful to the following practices, where the user will need that ratio to know thePRACTICES MANUAL edibe ices Date: March 2009 Pg: 14/27 concentration from the conductimeter. For this practice, it is necessary to prepare NaCl solutions at different concentrations. For this, the user comes from a NaCl 2 M solution, which will have to be diluted in known concentrations. The conductivity cell is put in the different solutions and the user makes a note of the conductivity value, which shows the conductimeter. This practice will have to be made for all the solutions with which the user will work using the unit. jon of Fick’s Law for the determination of 7.3.3 PRACTICE 1. Applic: diffusivity 7.3.3.1 Objective To study the diffusion of a solute in a liquid solvent (distilled water). 7.3.3.2 Necessary elements Unit QDTL of Edibon * Sodium chloride ¢ Achronometer * Practice development The cell is filled up with a NaCl 2M solution (1179/1). Fill up completely the cell and clean up any excess from the solution of the cell outside and from the capillary ends using filter paper.PRACTICES MANUAL edio — & @ = — -€0l Unit ref.: QDTLIQDTLC | Date: March 2009 Pg: 18/27 Put the cell in its position within the receptacle, Fill up the receptacle of the measurement unit with distilled water (approximately 1.5 L or 2 L). The distilled water level must surpass 5 mm above the diffusion cell. Afterwards, the magnetic stirrer will be turned on at a not very quick speed. Later, the conductimeter will be turned on and the user will start measuring the conductivity, for example, every 30 seconds. As it has been said before, the solution concentration will be determined - indirectly from the conductivity datum. The expression used will be the following: dk _D,-N a-D?-M-Cy dt AV ex where: “ Conductivity variation speed regarding time M Molarity of the saline solution - N Number of capillary x Capillary length D Diameter of a capillary V Distilled water volume Cy, Conductivity variation UL Thus, if the conductivity regarding time is represented, it is possible to obtain the diffusion coefficient or diffusivity from the slope.PRACTICES MANUAL Date: March 2009 Pg: 16/27 7.3.4 PRACTICE 2. Effect of the concentration in the diffusivity 7.3.4.1 Objective To study the influence of the concentration about the diffusivity. 7.3.4.2 Necessary elements © Unit QDTL of Edibon * Sodium chloride * A chronometer 7.3.4.3 Practice development To study the influence of the concentration on the diffusivity, several diffusion experiments will be made, changing from one to another the concentration ~ of the saline solution initial contained in the cell. Make the previous practice, coming from the solution saline 2M, 1.5M y Represent graphically los profiles of concentration in comparison with time.