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Experiment # 4: Distribution ARGAMINO, Cristian Ryan A. BLANCO, Joanne G. Group # 4, Chem 157.1, Mr. Vedad May 3, 2011 I.

Abstract

The Nernst Distribution Law states that if a solute X distributes itself between two immiscible solvents A and B at constant temperature and X is in the same molecular condition in both solvents, the ratio of the concentration of X in the two layers is a constant. In this experiment, acetic acid was used as the substance that will distribute itself in two immiscible liquids, i.e., water and diethyl ether. Liquid-liquid extraction, a process that separates components between two immiscible liquids, was employed. Different concentrations of acetic acid were added with diethyl ether and separated using separatory funnel. The layers were titrated with 0.1 M and 0.5 M NaOH to determine the partition coefficient K. The results have shown that for 0.5 M 1.0 M concentration, K=3.0494 and n = 0.69035 and for 0.25 M 0.5 M concentration, K = 2.943 and n = 0.72492. The results would tell us that acetic acid does not dissociate in water, however, theoretically it does. II. Keywords: Nernst Distribution Law, immiscible liquids, association, dissociation, extraction III.Introduction Liquid-liquid extraction uses the solubility differences of these molecules to selectively draw the product into the organic layer. Although the two layers are immiscible, isolation can be performed. Extraction can be used to separate or partition ionic or polar low- Liquid-liquid extraction uses the Liquid-liquid extraction uses the solubility differences of these molecules to selectively draw the product into the organic layer. Although the two layers are immiscible, isolation can be performed. Extraction can be used to separate or partition ionic or polar low-molecular-weight substances into an aqueous phase and less polar water-insoluble substances into an immiscible liquid organic phase. This is governed by the distribution coefficient. The distribution or partition coefficient is a quantitative measure of the how solute will distribute between aqueous and organic phases is called the distribution or partition coefficient. It is the ratio, K, of the solubility of solute dissolved in the organic layer to the solubility of material dissolved in the aqueous layer. (Note that K is independent of the actual amounts of the two solvents mixed.) This equation is derived from the Nernst Distribution Law. The Nernst Distribution Law states that if two liquids (or solids) a and b are partially immiscible and if there is a third component i present in both phases which behaves individually as an ideal solute (i.e., if it is sufficiently dilute), the ratio of its concentration c is independent of the individual values of c. [c(i)a/c(i)b] = constant
Chem 27.1, Gravimetric Analysis

However, this equation is only true if the solute acts as a simple molecule between the two solvents. This is no longer constant solute deviates and associates or dissociates in the solvent. The case may be that n molecules of the solute associates in solvent B. Applying the Mass Law: nX Xn

This equation is employed, C3n/C2=Kd Where C3 is the concn of X in A while C 2 is the concn of Xn in B. On the other hand, dissociation gives this equation: X A+B (1-x) x x Hence, the concn of the undissociated molecules in B is C2 (1-x). Applying the Distribution Law, we have: [C1/C2(1-x)]=Kd The objective of this experiment is to determine the values of K and n in the distribution of acetic acid between water and diethyl ether. IV. Methodology The experiment starts by preparing 60 mL serial dilution of each of the following from 17 M glacial acetic acid: 1.0M, 0.50 M, and 0.25 M. First, 120
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mL of 1.0 M solution was prepared from 17 M glacial HOAc. Next, 120 mL 0.5 M solution was prepared from 1.0 M solution. Finally, 0.25 M was prepared by from the 0.5 M solution. Volumes of the HOAc and water were then calculated to prepare the solutions. Twenty-five ml of the 1.0 M solution was pipeted into a separatory funnel together with 25 ml of diethyl ether. After shaking and letting it stand for 10 minutes (or until layers are completely separated), the aqueous layer was drawn into a clean container. Five ml was pipeted into a clean 125 ml erlenmeyer flask, before titrating with 0.50 M NaOH solution to a phenolphthalein endpoint for two trials. The same procedure was done with ether however, 0.10 M NaOH solution was used as the titrant. For 0.50 M and 0.25 M acetic acid solutions the previous procedures were applied. It was noted however to use, 10 ml aqueous solutions for titrations for both concentrations. After the titration, the concentration of acetic acid in each solution were calculated. Data obtained were used to determine the values of K and n for the concentrations used by the equation: K = C2n / C1 where: C2 = concentration of the solute in the aqueous solution C1 = concentration of solute in the organic solvent n = ratio of the average MW of the solute in solvent 1 to that in solvent 2 The results were recorded in a table afterwards. V. Results Serial Dilution:

Table 1. Data for 1 M acetic acid Volume of SOLVENT TRIAL NaOH (mL) 1 15.6 Water 2 15.4 Average 1 31.9 Ether 2 31.8 Average -

Concn of NaOH (M) 0.4664 0.4664 0.0823 0.0823 -

Volume of solution (mL) 10 10 10 10 -

Concn of solution (M) 0.727584 0.718256 0.72292 0.262537 0.261714 0.262126

Table 2. Data for 0.5 M acetic acid Concn Vol of of SOLVENT TRIAL NaOH NaOH (mL) (M) 1 7.6 0.4664 Water 2 7.7 0.4664 Average 1 20.2 0.0823 Ether 2 18.3 0.0851 Average Table 3. Data for 0.25 M acetic acid Volume Concn of of SOLVENT TRIAL NaOH NaOH (mL) (M) 1 3.8 0.4664 Water 2 3.9 0.4664 Average 1 11 0.0851 Ether 2 12 0.0851 Average Table 4. Values of K and n Concentration K range 0.5 1.0 M 3.0494 0.25 0.5 M 2.943 Computations:

Vol of solution (mL) 10 10 10 10 Volume of solution (mL) 10 10 10 10 -

Concn of solution (M) 0.354464 0.359128 0.356796 0.166246 0.155733 0.16099

Concn of solution (M) 0.177232 0.181896 0.179564 0.09361 0.10212 0.097865

n 0.69035 0.72492

Chem 27.1, Gravimetric Analysis

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Figure 1. Illustration of serial dilution done on concentrated (17.4 M) glacial acetic acid First, the volume of concentrated glacial acetic acid (17.4 M) needed to make 100 mL of 1.0 M solution was computed (see computations on results). A 5.7471 mL of the concentrated solution was obtained and diluted to 100 mL to obtain the 1.0 M. It was further diluted to obtain the 0.5 M and 0.25 M concentrations. At the same time, 0.1 M and 0.5 M of NaOH solutions were prepared by diluting 1.0 M NaOH. The formula was also used. Dilution of available NaOH solution was done due to lack of NaOH pellets in the laboratory. The solutions were standardized with potassium hydrogen phthalate (KHP) and were found to be 0.0823 M, 0.0851 M (2nd solution prepared for 0.1 M) and 0.4664 M. After this, 25 mL of the 1.0 M solution was mixed with 25 mL of diethyl ether in a separatory funnel. The mixture was shaken well and was left for about 15 minutes to let the layers separate. This was done to let the acetic acid distribute itself between the two solvents. The aqueous and organic layers were thenwithdrawn and titrated to the phenolphthalein endpoint with 0.5 M and 0.1 M NaOH, respectively, to compute the concentration of acetic acid present in the layers. This step was repeated for 0.5 M and 0.25 M acetic acid. The system water-diethyl ether-acetic acid form a system in which two immiscible solvents come in contact with each other and a third substance is introduced in small amounts so that it would distribute itself in the two immiscible layers. In this experiment, the acetic acid acts as the third substance that distributes itself between water and diethyl ether. The ratio of the mole fractions of the solute in the two liquids is found to be constant. This concept is the Nernst Distribution Law or the Partition Law. The Nernst distribution law states that, at equilibrium, the ratio of the concentrations of a third component in two liquid phases is a constant. This law is one of the laws applying to ideal dilute solutions. It can be derived from the partial molar free energy of the two solutes (A and B) in the two liquids given by: A =A + RT lnaA (Eq1) B =B + RT lnaB(Eq2) At equilibrium at constant temperature and pressure A = B, so combining equations 1 and 2 gives A + RT lnaA= B + RT lnaB(Eq3) Rearranging the equation gives:
Chem 27.1, Gravimetric Analysis Page 3 of 5

VI. Discussion In the first part of the experiment, serial dilution for glacial acetic acid was employed to produce different concentrations. This is a stepwise dilution of a substance in a solution, wherein an aliquot of the original solution with known concentration is diluted to produce another concentration of lower value.

A- B = RT lnaB- RT lnaA ln (aB/ aA) = (A- B)/RT (Eq4) ln (aB/ aA) = constant The right hand side of the equation becomes constant: a B/ a A= K (Eq5)

If acetic acid dissolves in diethyl ether without a change in molecular form and in water with partial association or dissociation, the distribution coefficient will be given by the total concentration in the second solvent (water) divided by the concentration of unassociated molecules in the first solvent (ether) according to the equation:

In more concentrated solutions, activities must be employed to obtain a true constant for the partition coefficient. Finally, the equation becomes: CB/CA = K (Eq. 6) Where: CB = concentration of aqueous layer CA = concentration of organic layer K = distribution constant when the solution is dilute or when it behaves ideally. The activity is essentially equal to the concentration C. In the experiment, the partition coefficient of acetic acid between water and diethyl ether was computed. Some factors affect the partition coefficients of substances such as the nature of solutes and solvents involved, concentrations, temperature and the manner at which the constant is written. It has also some limitations. One is that it is only applicable to dilute solutions where the ratio of the activities approaches 1. Another is that the law in its simple form is not applicable when substance encounters association or dissociation. Acetic acid is a weak acid that dissociates in water. For such solutes, which dissociate into ions or associate into a more complex molecule, the simple form of the Nernst Distribution Law will not be applicable anymore to the total concentrations of the two layers but instead, to the concentrations of the species common to both. In this case, the distribution law accounts for the activity of the species found in both of the layers.

where CB = concentration of the solute in the aqueous solution CA= concentration of the solute in the organic solvent n = ratio of the average molecular weight of the solute in solvent A to that in solvent B The value of n accounts for the association and dissociation of acetic acid in the aqueous layer. If the solute dissociates in aqueous solution, its average molecular weight in water decreases and n is greater than 1. If the solute associates in water solution, its average molecular weight in water increases and n is less than 1. Based on the results of the experiment, both the computed n are less than 1. However, this should not be the case because acetic acid tends to dissociate in water, theoretically. VIII. Conclusion and Recommendations The Nernst Distribution Law governs the activity or concentration of a solute as it distributes in a immiscible solvent system. The equation, CB/CA = K, is only applicable if the solution is dilute or behaves ideally. Deviation from this behavior is due to some limitations the holds true for the law. In this experiment, the solute encounters association/ dissociation which entail raising the concentration of the aqueous layer CB to an exponent n which accounts for the association and dissociation of acetic acid in the aqueous layer. The value of n>1 was expected due to acetic acids tendency to dissociate in water. The error could be attributed to the incomplete separation in the separatory funnel or miscalculations of concentrations from the serial dilutions to the titration processes employed. IX. References I hereby certify that I have given substantial contribution to this report. Joanne G. Blanco
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Figure 2.Ball-and-stick model of the dissociation of acetic acid to acetate. A water molecule is protonated to form a hydronium ion in the process. The acidic proton that is transferred from acetic acid to water is labelled in green.

Chem 27.1, Gravimetric Analysis

Cristian Ryan A. Argamino

ANSWERS TO GUIDE QUESTIONS: 1. Does acetic acid dissociate or associate in water? Why? The results of the experiment show that acetic acid does not dissociate in water. However, this should not be the case because acetic acid tend to dissociate into hydrogen and acetate ions. Water, which is a better base than acetate, has a higher affinity for hydrogen ions. Due to this, hydrogen leaves acetate and joins water to form hydronium ions. 2. How does dilution affect dissociation or association of acetic acid in water? Explain.

Dilution increases the dissociation of acetic acid. This is due to the fact that the solute-solvent interaction becomes greater than solute-solute interaction after dilution. That is, when it is more solvated, electron repulsion is greater so it tends to dissociate more.

Chem 27.1, Gravimetric Analysis

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