Diploma in Chemical Process and Technology (Food Technology) Basic Instrumental Analysis CP4009 Experiment 1 : Solvent Extraction

Lee QuanHan 0523437 2A/23 12/11/06

Synopsis
Solvent extraction is a method to separate compounds based on their solution preferences for two different immiscible liquids, usually water and an organic solvent. It is an extraction of a substance from one liquid phase into another liquid phase. There are some certain factors that affect the effectiveness of solvent extraction

Solvent selection Extraction Conditions Mode of Operation Different Type of Extractants

The result for the absorbance values is shown here, Table 1. Values of Absorbance Absorbance pH Molybdenum (x) Nickel (y) Blank (z)
1 2 3 4 6 8 0.4642 0.6608 0.6861 0.7690 0.6302 0.1944 0.1230 0.0209 0.2612 0.4138 2.0148 2.0195 0.0066 0.0142 0.043 0.0324 0.0476 0.0681

M = (x - z)
0.3412 0.6399 0.4249 0.3552 -1.3846 -1.8251

N = (y - z)
0.1164 0.0067 0.2182 0.3814 1.9672 1.9514

But during the experiment, Errors occurred and the results was incorrect, Table 1 results was gotten from another group. This might due to the impurity of the nickel complex solution we used or the complex had been diluted or contaminated. Others reason might be due to human errors of adding too much agents or pH buffer solution or the time taken for them to attain equilibrium was too short as some solvent extraction required more than 1 hour to equilibrium depending on the pH and the conditions. Therefore, the experiment was not successful even though the objectives were met.

Objectives
To obtain qualitative extraction curves for metal oxinates in chloroform. To practice in makin proper spectroscopic measurements involving organic solvents.

Introduction
Solvent extraction is a method to separate compounds based on their solution preferences for two different immiscible liquids, usually water and an organic solvent. It is an extraction of a substance from one liquid phase into another liquid phase. In an industrial application, this process is done continuously by pumping an organic and aqueous stream into a mixer. This mixes the organic (oil like solution) component with the aqueous ( water based solution) component. This contacts the two liquids to allow ion transfer between them. The mixing continues until equilibrium is reached. The size of the mixers are such that sufficient residence time is allowed for, to reach equilibrium. Once the ion transfer is complete (equilibrium is reached) , the mixture flows into a swimming pool type vessel, where the organic and aqueous are allowed to separate, similar to the way oil and water would separate after mixing them. A distribution ratio is often quoted as a measure of how well-extracted a species is. The distribution ratio (D) is equal to the concentration of a solute in the organic phase divided by its concentration in the aqueous phase. Depending on the system, the distribution ratio can be a function of temperature, the concentration of chemical species in the system, and a large number of other parameters. D = (all species of solute in organic phase)/(all species of solute in aqueous phase)

CHLOROFORM A trichloromethane and methyl trichloride, is a chemical compound with formula CHCl3. (figure 1)It does not support combustion in air, although it will burn when mixed with more flammable substances. It has a density of 1.48 g/cm and is an organic compound. Because of the Cl- atoms of high reactivity, this organic compound can exchange metal ions with metals.

CHCl3 (Figure 1)

8-HYDROXYQUINOLINE Chelating agent removes a metallic ion from a solid salt and holds it in solution. By forming a soluble complex from an insoluble compound it is possible to remove unwanted material, washing it away with water. The agent is an electron-pair donor and the metal an electron-pair acceptor, this is known as co-ordination bonding. The functional groups of the agent can be acidic or basic. When they react, an acidic group loses a proton and coordinates with a metal atom which is the exchanging of ions. In this experiment, hydroxyquinoline was the chelating agent, it react with the Nickel atoms in the Nickel complex and transfer into the organic layer(cholorform) An example of an chelating agent is shown on figure 2. It hold the metals ion tightly so it wont collapse under the organic layer forming ppt.

Figure2 (red colour = metal ions) (black colour = ethylenediaminetetraacetic acid)

SODIUM SULFATE It is a compound of Sodium and is anhydrous. chemically very stable, being unreactive toward most oxidising or reducing agents at normal temperatures. At high temperatures, it can be reduced to sodium sulfide. It is a neutral salt, which forms aqueous solutions with pH of 7. It is used to absorb the pH buffer solution which contain water when filtering. To optimize the extraction process, there are some certain factors that are needed to be controlled.

Solvent selection Extraction Conditions Mode of Operation Different Type of Extractants

Solvent Extraction Solvents differ in their extraction capabilities depending on their own and the solutes chemical structure. The distribution coefficient and selectivity are the most important parameters that govern solvent selection. The desired properties of solvents are a high distribution coefficient, good selectivity towards solute and little or no miscibility with feed solution and the solvent should be easily recoverable for recycle. Designing an extractor is usually a fine balance between capital and operating costs. Usually, good solvents also exhibit some miscibility with feed solution. Consequently, while extracting larger quantities of solute, the solvent could also extract significant amount of feed solution. Extraction Conditions The temperature, pH and residence time could have an effect on the yield and selectivity. Operating pressure has a negligible affect on extraction performance and therefore most extractions take place at atmospheric pressure unless restricted by vapor pressure considerations. Temperature can also be used as a variable to alter selectivity. Elevated temperatures are sometimes used in order to keep viscosity low and thereby minimizing mass-transfer resistance. Other parameters to be considered are selectivity, mutual solubility, precipitation of solids and vapor pressure. The pH becomes significant in metal and bio-extractions. In bio-extractions (e.g., Penicillin) and some agrochemicals (e.g. Orthene), pH is maintained to improve distribution coefficient and minimize degradation of product. In metal extractions,

kinetic considerations govern the pH. In dissociation-based extraction of organic molecules, pH can play a significant role (e.g., cresols separation). Sometimes, the solvent itself may participate in undesirable reactions under certain pH conditions (e.g., ethyl acetate may undergo hydrolysis in presence of mineral acids to acetic acid and ethanol). Residence time is an important parameter in reactive extraction processes (e.g., metals separations, formaldehyde extraction from aqueous streams) and in processes involving short-life components (e.g., antibiotics & vitamins) Mode of Operation Cross-Current Operation Crosscurrent mode is mostly used in batch operation. Batch extractors have traditionally been used in low capacity multi-product plants such as are typical in the pharmaceutical and agrochemical industries. For washing and neutralization operations that require very few stages, crosscurrent operation is particularly practical and economical and offers a great deal of flexibility. The extraction equipment is usually an agitated tank that may also be used for the reaction steps. In these tanks, solvent is first added to the feed, the contents are mixed, settled and then separated. Single stage extraction is used when the extraction is fairly simple and can be achieved without a high amount of solvent. If more than one stage is required, multiple solvent-washes are given. Though operation in crosscurrent mode offers more flexibility, it is not very desirable due to the high solvent requirements and low extraction yields. Counter-Current Operation For larger volume operation and more efficient use of solvent, countercurrent mixersettlers or columns are employed. Countercurrent operation conserves the mass transfer driving force and hence gives optimal performance. The dimensionless term mS/F, included in all the above equations, is called the extraction factor (E), and is an important parameter in the design of extraction processes. For a given number of stages, the higher the E factor, the higher is the reduction ratio and easier is the extraction. Systems with E of less than 1.3 are not likely to be commercially feasible. Different Types of Extractant Different Types of Extractants determine how well the extraction yield. It affect the time taken, the solubility, pH values and selectivity(product purity). Below are 5 main extractants and its advantages and uses. Extractants are used because it is necessary to form a chemical compound (= complex) with the solute and thus make it soluble in the organic phase.

Chelating Agents Main commercial extractants for copper Operate on hydrogen ion cycle. Function with acid and ammoniacal leach solutions More selective than other extractant classes Kinetically slower than ion pair extractants Have good physical properties in terms of phase separation, low aqueous solubility, chemical stability Ions-Pair Extractants Commercial extractants for uranium, thorium, vanadium, gold, cobalt and other metals Kinetics, both extraction and stripping are fast Extraction is usually of a metal anion complex Selectivity is not high. Other anions can compete with the metal being extracted Selectivity can be pH dependent Neutral / Solvating Extractants Kinetically fast Extract neutral metal complexes Selectivity is low Organometallic complex must be organic soluble Organic Acid Extractants Operate on a hydrogen ion cycle but do not display hydrogen ion stoichiometry. Selectivity is poor and careful pH control may be required to achieve reasonable selectivity Ligand Subtitution Extractants Extraction is not pH sensitive Stripping(transfer of the metal back into a second pure aqueous phase for winning or further processing) is by decomposition of the metal ligand chloride complex at relatively low chloride ion concentration Selectivity can be very high and is based to an extent on extraction kinetics

Results and Calculations

Table 1. Values of Absorbance pH Molybdenum (x)
1 2 3 4 6 8 0.4642 0.6608 0.6861 0.7690 0.6302 0.1944

Absorbance Nickel (y) Blank (z)

0.1230 0.0209 0.2612 0.4138 2.0148 2.0195 0.0066 0.0142 0.043 0.0324 0.0476 0.0681

M = (x - z)
0.3412 0.6399 0.4249 0.3552 -1.3846 -1.8251

N = (y - z)
0.1164 0.0067 0.2182 0.3814 1.9672 1.9514

Graph of Absorbance
2.5 2 1.5 1 0.5 [M] [N] 0 -0.5 0 -1 -1.5 -2 -2.5 pH 2 4 6 8 10 Molybdenum [M] Nickel [N] Poly. (Nickel [N]) Poly. (Molybdenum [M])

Discussion
During this experiment, errors occurred and we couldnt get the correct results of the absorbance readings. For the nickel reading, at pH 6 8 the yield should be the highest and the adsorbance reading should be high, but our result shown negative values as shown in (Figure 3)

Absorbance pH Nickel (y) 1 1.9155 2 2.1421 3 1.0296 4 0.8190 6 -0.046 8 -0.085 Figure 3 This might due to the impurity of the nickel complex solution we used or the complex had been diluted or contaminated. Others reason might be due to human errors of adding too much agents or pH buffer solution or the time taken for them to attain equilibrium was too short as some solvent extraction required more than 1 hour to equilibrium depending on the pH and the conditions. On the correct reading of the absorbance, the graph readings show that Nickel is yield much higher than Molybdenum. This show that the chelating agent used is more effective for Nickel compare to Molybdenum as the agent is used to chelate the metal ions for extraction. At pH 2.8, both metals complex was extract equally while at pH 2 and 8, Molybdenum and Nickel has the highest yield respectively. During the filtering of the organic layer containing the metal ions through sodium sulphate, it is observed that some of the sodium sulphate had drop into the tubes as due to lack of cotton wool to cover or too much of sodium sulphate was added. In the end, the filtered organic solvent was contaminated with sodium sulphate and during the reading of the absorbance, it reach very high reading as lights cant pass through opaque matters. This might be another reason why our reading were incorrect. This experiment is how pH affect the extraction of the metal ions since different pH was used. For an example of pH,

CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH2-COOH

At low pH where there is a high concentration of H+, the pressure is to keep the hydrogen from ionizing. This compound is thus dominated by the long hydrocarbon chain and is essentially non-polar despite some effect of the weakly acidic carboxyl group.

At high pH and low H+, ionization is favored. This leaves a charged group to dominate and makes the compound essentially polar. By switching from one pH range to another, the compound changes its polarity and its preference for residing in either a polar or nonpolar solvent. Therefore, Higher pH, ionization of nickel ions is the best, yielding the highest results. At low pH, the yield was zero or negative results.

5.2 Define Distribution Coefficient and Distribution Ratio. A Distribution coefficient is a measure of differential solubility of a compound in two solvents. The logarithmic ratio of the concentrations of the solute in the solvent is called log P (sometimes LogP). A Distribution ratio is measure of how well-extracted a species is. The distribution ratio (D) is equal to the concentration of a solute in the organic phase divided by its concentration in the aqueous phase. It can be a function of temperature, the concentration of chemical species in the system, and a large number of other parameters. 5.3 What is a chelation complex and what is an ion-association complex. A chelation complex is a complex that contain chelating agent and metal ions. The agent bind the metal ions in it (Figure 2), the agent donate an unbounded electrons pair to the metal while taking in the metal ion. Ion-association complex also has something to do with ions in similar ways as chelation complex as it also exchange ions to bind each other tightly. 5.4 What is the function of 8-hydroxyquinoline and what happen if addition of 8hydroxyquinoline is omitted. 8-hydroxyquinoline act as a chelating agent which react with metal ions. If the addition of this is omitted, the experiment testing of nickel metals will have no results since theres no agent to bind the nickel ions and dissolve into the organic layer. 5.5 What are some factors that can affect the solvent extraction of metal chelates. Some factors are pH, Temperature and the chelating agents used. The pH affect as in nickel extraction, when acidic, the chelates cant bind most of the metal ions as it is incomplete extraction. In netural pH, the yield of nickel extraction was the highest.

If the temperature of the extraction is very high to cope with the high boiling point of solvent, the agents might break down to form other compound which will not chelate with the metal ions Different chelating agents are used for different metals. If used wrongly, the extraction might be very slow or little or even no results. 5.6 Explain from the graph, over what range of pH is possible to separate (a) nickel ion from molybdenum ion in aqueous solution (b) molybdenum ion from nickel ion in aqueous solution From the graph, the yield of [M] ions is highest at pH 2. while the highest yield of [N] ions is at pH 8. To separate [N] ions from [M] ions, the best range of pH is 6.5 to 8, in the netural range. To separate [M] ions from [N], the best range from the graph would be 1.5 to 2 as the yield of [M] is highest while yield of [N] is zero. 5.7 What is the purpose of conducting assignment 3. Assignment 3 is to conduct the reagent blank as this experiment is about measuring absorbance which UV-VIS spectrometer is used. The spectrometer measure the amount of light wave that cant pass through the solvent and calculate out the absorbance of the solvent. There is other compounds other than the metal ions in the solvent. So if the blank is not carried out, the absorbance value will not be accurate as it also include the absorbance of other substances in the cell.

Conclusion
This experiment was not successful as the readings for the absorbance was incorrect for nickel and molybdenum ions due to different errors that might cause it. The objectives of this experiment was met as the correct results was taken from another groups absorbance reading.

Reference
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