ABSTRACT In liquid-liquid extraction (LLE) experiment, it is divided into two parts.

For the first part, it is to determine the coefficient distribution for the organic solvent which solvent is water and solution is propionic acid. As for the second experiment, the objective is to determine the mass transfer coefficient. In the first part, mixture of organic solvent with de-mineralised water that mixture has been separated to the organic and aqueous layer. Titration method is used with 0.1M of sodium hydroxide from the upper and bottom layer sample. The experiment is repeated by using 3ml of propionic acid and 1ml of propionic acid. By titration with 0.1M sodium hydroxide, the values of coefficient distribution (K value) are 1.672 in 5ml of propionic acid, 2.175 in 3ml propionic acid and 3.600 in 1ml propionic acid. In experiment part two, 50 mL sample from feed (V13), raffinate (V11) and extract (V1) stream are taken. The samples then are titrated with 0.1M NaOH and 0.025M NaOH. Propionic acid extracted from the organic phase is 0.032mol/min while propionic acid extracted from the aqueous phase is 0.013mol/min. Next, the mass transfer coefficient value when titrated with 0.1M NaOH is 385858.43kg/min. The experiment is conducted and completed successfully.

INTRODUCTION Liquid-liquid extraction (LLE) is a method used for the separation of a mixture using two immiscible solvents which is widely used in chemical, petroleum refinery, pharmaceutical, mining and nuclear industries. The ability of LLE to separate compounds in a mixture depends on how differently the compounds of the sample mixture partition themselves between the two immiscible solvents. There are a few characteristics that may be considered in choosing the solvent for LLE. Solvent would if possible completely dissolve both compounds in the mixture. In fact, the solvent selected must be immiscible with the first solvent. Next, second solvent should dissolve only one component of the original mixture.(University of Alberta, Faculty of Science Chemistry,2013) In LLE, mixture is dissolved or suspended in the first solvent before it is introduced to the second solvent. One component of the mixture will be transferred into the second solvent by shaking the solvent together in an apparatus called a separator funnel and thus would leave the other component in the first solvent. By using separator funnel, final separation of two solvents is accomplished, followed by evaporation of solvents, produces the separated components. Two phases must be brought into contact to permit transfer of material in gas absorption and distillation and then be separated. Extraction equipment may be operated batch wise or continuous. The extract is the layer of solvent with extracted solute and the raffinate is the layer from which solute has been removed. The extract may be lighter or heavier than the raffinate, and the extract may be shown coming from top of the equipment in some cases and from the bottom in others. The operation may be repeated if more than one contact is required, but when the quantities involved are large and several contacts are needed, continuous flow becomes economical. Separation will result if the components of the original solution distribute differently between the two liquids. There are two major differences although the component balances will be essentially identical to those for leaching, which is the carrier phase is a liquid instead of solid, so the physical separation technique will change and two distinct phases develop so that simplicity of uniform solution is lost.

OBJECTIVE There are objectives for this experiment: To determine the coefficient distribution for the organic solvent which solvent is water and solution is propanoic acid. To determine the mass transfer coefficient.

THEORY The solvent (water) and solution (organic solvent/propionic acid) are mixed together and then allowed to separate into the extract phase and the raffinate phase. The extract phase will be water and propionic acid and the raffinate, organic solvent with a trace of propionic acid. In dilute solution at equilibrium, the concentrations of the solute in the two phases are called the distribution coefficient or distribution constant K. The distribution coefficient, K, is defined as the ratio: K= Y/X Where Y is the concentration of the solute in the extract phase whereas X is the concentration of the solute in raffinate phase. The distribution coefficient can also be expressed as the weight fraction of the solute in the two phases in equilibrium contact: K = y/x Where y is the weight fraction of the solute in the extract and x is the weight fraction of the solute in the raffinate. It is assumed that equilibrium exists between the two phases. At low concentrations, the distribution coefficient is dependent on the concentration and thus Y= KX The rate at which a soluble component is transferred from one solvent to another will be dependent, among other things, on the area of the interface between the two immiscible liquids. Therefore it is very advantageous for this interface to be formed by droplets and films, the situation being analogous to that existing in packed distillation columns.

The theory for the system Trichloroethylene-Propionic acid-Water is as follows: Let Vw Vo X Y : Water flow rate, lt/s : Trichloroethylene flow rate, lt/s : Propionic acid concentration in the organic phase, kg/lt : Propionic acid concentration in the aqueous phase, kg/lt

Mass Balance : Propionic acid extracted from the organic phase (raffinate). =Vo(X1X2) .................(3) Propionic acid extracted by the aqueous phase (extract) =Vw(Y10) ..................(4) Therefore theoretically, Vo(X1X2) = Vw(Y10) ...................(5)

Mass transfer coefficient:

( ( ) )

......................(6)

where Log mean driving force : (X1-X2) / ln (X1/X2) X1 : Driving force at the top of the column = (X2 - 0) X2 : Driving force at the bottom of the column = (X1-X1*)

where X1* and X2* are the concentrations in the organic phase which would be in equilibrium with concentrations Y1 and Y2 ( = 0.0) in the aqueous phase, respectively. The equilibrium values can be found using the distribution coefficient for the chemicals used (Assume that Y=KX relation holds at equilibrium for a constant K). Rate of acid transfer may be calculated using Equation (3) or (4) based on raffinate or extract phases, respectively. It is normal to operate a column so that the continuous phase 'wets' the packing. If the packing is 'wetted' by the dispersed phase then coalescence will be increased and the mass transfer/unit volume will be reduced. The rate of mass transfer of a solute from one phase to another is normally increased with greater throughput of material, because of increased turbulence giving better mixing. There is however, a limit to the maximum amount of material that can be fed through the column. The limit is called the 'Flooding Point' and occurs at specific flow rates of constituents resulting in one of the phases being rejected from the column.

APPARATUS AND MATERIALS

Experiment A 1) 250ml Conical stoppered flask 2) 250ml Measuring cylinder 3) 250ml Separating funnel 4) Pipette with rubber bulb 5) Sodium Hydroxide Solution (0.1M) 6) Propionic acid

Experiment B

EXPERIMENTAL PROCEDURE Experiment A 1) 50ml of organic solvent is being mixed with 50ml of de-mineralised water in conical flask. Then 2ml of propionic acid is added to the mixture. 2) A stopper is placed into the flask and the mixture is shaken for 5 minutes. 3) The mixture is then poured into the separating funnel for 5 minutes and removed the lower aqueous layer. 4) 10ml of the sample is titrated against 0.1M NaOH using phenolphthalein as the indicator. 5) The experiment was repeated using the different concentration of the propionic acid.

Experiment B 1) 100ml of propionic acid are added to 10 litres of organic phase. The mixture is then filled into the organic phase tank (bottom tank).

2) The level control is switched to the bottom of the column by keeping the bottom electrodes on (the S2 valve is switched on). 3) The water feed tank is filled with 15 litres of clean de-mineralised water (the V13 valve was open). The water feed pump is started (valve S3) and the flow rate of water is regulated to the maximum by opening valve C1. 4) The flow rate is reduced to 0.21 litre/min as soon as the water reaches the top packing. 5) The metering pump (S4) is started. 6) Steady conditions must be achieved by running the set up for 15-20 minute. The flow rate is monitored during the period to ensure that they remain constant. 7) Two or three batches of 30ml sample are taken from the feed, raffinate and extract streams (valve V1). 8) 10ml of each sample is titrated against 0.025M NaOH using phenolphthalein as the indicator (to titrate the feed and raffinate continuous using magnetic stirrer may be needed.

RESULTS EXPERIMENT A Aqueous Layer Propionic acid added (mL) Titre of M/10 NaOH (mL) Concentration (M) Titre of M/10 NaOH (mL) Organic Layer Concentration (M)

79.9

0.799

47.8

0.478

1.672

52.0

0.520

23.9

0.239

2.175

18.0

0.180

5.0

0.050

3.600

EXPERIMENT B Flow rate of aqueous phase (L/min) Flow rate of organic phase (L/min) Sodium hydroxide concentration (M) Feed (mL) Raffinate (mL) Extract (mL) Propionic acid extracted from the organic phase (mol/min) Propionic acid extracted from the aqueous phase 0.013 0.032 6.2 21.2 4.59 x 10-3 15.9 0.4 54.0 0.8 0.0117 2.96 x 10-4 0.1 M 0.025M Concentration of Propionic acid (kg/L) 0.21 0.21

(mol/min)

Mass transfer coefficient (kg/min) 385858.43

CALCULATIONS

EXPERIMENT A CONCENTRATION M1V1 = M2V2 M1 = concentration of NaOH (M) M2 = concentration of Propionic Acid (M) V1 = Volume of NaOH (mL) V2 = Volume of Propionic Acid (mL)

K= distribution coefficient

1. For 5 mL Propionic Acid added a) Aqueous layer, Y M1V1 = M2V2 (0.1)(52.0) = M2 (10) M2 = 0.520 M b) Organic layer, X M1V1 = M2V2 (0.1)(23.9) = M2 (10) M2 = 0.239 M

2. For 3 mL Propionic Acid added a) Aqueous layer, Y M1V1 = M2V2 (0.1)(79.9) = M2 (10) M2 = 0.799 M

b) Organic layer, X M1V1 = M2V2 (0.1)(47.8) = M2 (10) M2 = 0.478 M

3. For 1 mL Propionic Acid added a) Aqueous layer, Y M1V1 = M2V2 (0.1)(18.0) = M2 (10) M2 = 0.180 M

b) Organic layer, X M1V1 = M2V2 (0.1)(5.0) = M2 (10) M2 = 0.050 M

EXPERIMENT B CONCENTRATION M1V1 = M2V2 M1 = concentration of NaOH (M) M2 = concentration of Propionic Acid (M) V1 = Volume of NaOH (mL) V2 = Volume of Propionic Acid (mL) 1. Concentration of Propionic Acid at feed (X1) M1V1 = M2V2 (0.1)(15.9) = M2 (10) M2 = 0.159 M MW of Propionic acid = 74 g/mol

M2 = 0.0117 kg/L 2. Concentration of Propionic Acid at raffinate (X2) M1V1 = M2V2 (0.1)(0.4) = M2 (10) M2 = 0.004 M MW of Propionic acid = 74 g/mol

M2 = 2.96 x 10-4 kg/L 3. Concentration of Propionic Acid at extract (Y1) M1V1 = M2V2 (0.1)(6.2) = M2 (10) M2 = 0.062 M

MW of Propionic acid = 74 g/mol

M2 = 4.59 x 10-3 kg/L Flow rate of aqueous and organic phase = 0.21 L/min Mass balance: Propionic Acid extracted from the organic phase (raffinate) = V0 (X1 X2) ( )( )

= 0.032 mol/min

Propionic Acid extracted from the aqueous phase (extract) = VW (Y1 0) ( )( )

= 0.013 mol/min

To calculate X1*, the average distribution coefficient from experiment A

K = 2.482

X1* = 1.85 x 10-3 ( X1 = X2 0 X2 = X1 X1* )

Log mean driving force = 2.73 x 10-3

Mass transfer coefficient (based on the raffinate phase)

)(

= 385858.43 kg/min

DISCUSSION This experiment is divided into two experiments. The objective for the first experiment was to determine the coefficient distribution for the organic solvent which solvent is water and solution is propionic acid. The main objective for the second experiment was to determine the mass transfer coefficient. For first experiment, we need to prepare a mixture of 5ml propionic acid, 50mL of water and 50mL of organic solvent (trichloroethylene) in a conical flask. Shake it for about 5minutes.Then transfer the mixture in a separator funnel. The mixture formed two layers which are upper layer and bottom layer. As what has been practiced in the experiment, the mixture of trichloroethylene-propanoic acid-water is separated by using separator funnel. When a compound is shaken in a separator funnel with two immiscible solvents, the compound will distribute itself between the two solvents. The bottom layer contains more water and the upper layer contains more propanoic acid as water is denser than the solvent We used titration method with 0.1M of sodium hydroxide from the upper and bottom layer sample. The experiment was repeated by using 3ml of propionic acid and 1ml of propionic acid. By titration with 0.1M sodium hydroxide, the values of coefficient distribution (K value) are 1.672 in 5ml of propionic acid , 2.175 in 3ml propionic acid and 3.600 in 1ml propionic acid. As the volume of propionic acid increases, the coefficient distribution value decreases.This shows that the greater the amount of solvent added, the higher the increase in distribution coefficient. Distribution coefficient defines as the ratio of the amounts of solute dissolved in two immiscible liquids at equilibrium. For the second experiment, which is to determine the mass transfer coefficient, we used the liquid-liquid extraction column to get the feed, raffinate and extract solution. The samples then were titrated with 0.1M NaOH and 0.025M NaOH. Propionic acid extracted from the organic phase was 0.032mol/min while propionic acid extracted from the aqueous phase was 0.013mol/min. Next, the mass transfer coefficient value when titrated with 0.1M NaOH was 385858.43kg/min. The mass transfer coefficient was high. Mass transfer coefficient important to determine factors in a solvent-solvent extraction system and also to determine the rate at which a solute is transferred from one phase to another (Ozioma Nawachukwu ,2013). A good extraction solvent needs four essential features: it

has to be practically immiscible with water, it has to have a different density to water, it needs good stability and volatility so that it can easily be removed from the organic compound by evaporation and the solute want to extract has to dissolve easily in it.(McCabe,2001) There might be some error occur during the experiment conducted. The value from this experiment might be different with the actual. This maybe because of several error occur during the experiment progress. The most common error is the position of the eye during taking the volume value at the burette, the eye position should be straight to the scale and must be perpendicular to the meniscus. We choose pinkish-purple color for the color indicator during titration, but to get all the same color might be hard enough to identify. As the color is not constant, the value of mass transfer coefficient and distribution coefficient will be different from the actual. The color indicates that the NaOH is at equilibrium with the sample solution. The differences of the experiment result from the actual result might also cause by the oil emission and impurities at the beaker, conical flask or burette. To avoid the error, the equipment or apparatus we use must be in clean condition. The concentration of propionic acid in raffinate is more than in extract. The concentration of propionic acid should more in extract than in raffinate, this might be the extraction process does not occur efficiently. More time needed to extract the solution. Moreover, the experiment should be repeated at least 3 times to get the accurate values and the mistake during the experiment progress can be identified.

CONCLUSION As a conclusion, the value for distribution coefficient can be determine by titration with 0.1M values are 1.672 in 5ml of propionic acid, 2.175 in 3ml propionic acid and 3.600 in 1ml propionic acid.As a result, the coefficient distribution value decreases when the volume of propionic acid increases.This shows that the greater the amount of solvent added, the higher the increase in distribution coefficient. The value of mass transfer coefficient from liquid-liquid extraction was 385858.43kg/min titrated with 0.1M NaOH. From this the concentration of propanoic acid appears to be the highest in extract phase.

RECOMMENDATIONS There are a few problems that occur during the experiments. To fix these problems, there are a few recommendations. Make sure that all apparatus are in good condition before run the experiment to avoid the error during the experiment is conducted. Make sure that the sodium hydroxide (NaOH) is titrated slowly during the titration process to get the correct color. Ensured that the eyes is perpendicular to the meniscus of the burette during the reading of burette is taken. Make sure that the propionic acid is measured correctly during the experiment to avoid the wrong result.

REFRENCES Lab Manual McCabe,W.L Smith,J.C and Harriot(2001),Unit Operations of Chemical Engineering,6th Edition.McGraw-Hill. Ozioma Nawachukwu ,(2013),Researchgate, Significance of mass transfer coefficient. Retrieved from: http://www.researchgate.net/post/What_is_the_significance_of_the_mass_transfer _coefficient_in_liquid_liquid_extraction University of Alberta, Faculty of Science Chemistry (2013), Theory of Separation. Retrieved from: http://www.chem.ualberta.ca/~orglabs/Interactive%20Tutorials/separation/Theory /theory0.htm

APPENDIX