Experiment 4: Distribution Dulos, Maiko Luz V. Montes, Jessica Marie V. Group 4, Chem 157.1, FEJ, Mr.

Geoffrey Li January 31, 2011 I. Abstract The Nernst distribution law states that at a given temperature, a substance will distribute itself between two solvents until at equilibrium the ratio of the activities of the substance in the two layers is constant. In this experiment, the distribution or partition coefficient (K) of acetic acid between water and diethyl ether was determined. Solutions of glacial acetic acid (1.0M, 0.50 M, 0.25 M), which were prepared using serial dilution, were mixed with diethyl ether in a separatory funnel. The separated layers (aqueous and organic) were then titrated with 0.50 M and 0.10 M NaOH respectively. It was calculated that the K and n values in the concentration range 0.50 M-1.0 M are 0.8567 and 1.8834 while for the 0.25 M- 0.50 M, they are 1.4769 and 1.3345 respectively. II. III. Keywords: Distribution/Partition coefficient Serial dilution Dissociate Associate Introduction In more concentrated solutions, activities must be used instead of concentrations to obtain a true constant for the partition coefficient. Some factors that may affect K are nature of the solute and the solvents involved, concentration, temperature and pressure and the manner at which the constant is written. The objective of this experiment is to determine the values of partition coefficient and n in the distribution of acetic acid between water and diethyl ether. IV. Experimental

When a quantity of solute, say X, is dissolved between two immiscible or partially immiscible liquids, the solute tends to distribute itself between the two liquid layers in such a way that at equilibrium, the ratio of the concentration or activity of the solute in the two layers is a constant at any given temperature. According to Nernst distribution law, the ratio of the activities of a solute X that is distributed between the two liquids at a given pressure and temperature is constant and will be equal to the Nernst partition coefficient (distribution constant) given by: where aB and aA is equal to the activity of the solute in the aqueous solution and organic solvent and the value of n determines whether the solute dissociates or associates in the aqueous layer. The distribution law is valid provided that: a. The solutions are ideal and dilute b. The presence of solute does not change the mutual solubility of the two layers c. The solute has the same molecular mass in both layers When the solutions are dilute or approaches ideality, the activity is essentially equal to the concentration C to give:

The value of n determines whether the solute dissociates or associates in the aqueous layer. Dissociation in water refers to the process of splitting or separation of the ionic compound intro smaller particles or ions plus the formation of hydronium. On the other hand, a hydrate is created when a substance associates with water to form a compound in which the water is present in its molecular form. Chem157.1, Distribution

By serial dilution, 60mL of each of 1.0M, 0.50M and 0.25M were prepared starting from glacial acetic acid. Serial dilution was done by preparing 100mL of 1.0M solution from glacial acetic acid which is 17.4M. Afterwards, another 100mL of the 0.5M solution was obtained from the 1.0M solution. Lastly, 100mL of the 0.25M solution from 0.50M was obtained. The volumes of acetic acid solution and water needed to prepare the desired solution were calculated. From NaOH pellets, 0.5M NaOH solution was prepared by diluting 200mL of 0.10M NaOH solution. From the 1.0M solution, 25mL was pipetted into a separatory funnel. Twenty five milliliters of diethyl ether was added and shaken. The solution was allowed to stand for 10 minutes or until the layers completely separate. The aqueous layer was drawn into a clean container wherein 5.0mL of it was transferred into a clean 125-mL Erlenmeyer flask. Ten milliliters of distilled water was added and the solution was then titrated with 0.50M NaOH to the phenolphthalein end point. Two trials were obtained. On the other hand, 10mL of the ether layer was transferred into another 125-mL Erlenmeyer flask and 10mL of distilled water was added to it. The solution was titrated with 0.10M NaOH to the phenolphthalein end point and 2 trials Page 1 of 5

were obtained. The preceding steps were repeated for the 0.50M and 0.25M concentrations of acetic acid solutions. Ten milliliters of the aqueous solutions were obtained for titration purposes. The concentration of acetic in each solution was calculated. Lastly, the values of K and n for the concentrations used were determined by the equation:

Computations: A. For concentration 0.5-1M

 

where C2 is the concentration of the solute in the aqueous solution, C1 is the concentration of the solute in the organic solvent and n is the ratio of the average molecular weight of the solute in solvent 1 to that in solvent 2. If the solute dissociates in aqueous solution, its average molecular weight in water decreases and n is greater than 1. If the solution associates in water solution, its average molecular weight in water increases and n is less than 1. Results from the experiments were tabulated and recorded. V.
Solvent water

B. For concentration 0.25-0.5M C.

Results
Trial 1 2 Ave 1 2 Ave VNaOH (ml) 7.35 7.35 XXX 26 27.5 XXX VNaOH (ml) 7.0 7.5 XXX 7.2 2.0 XXX VNaOH (ml) 3.42 3.50 XXX 2.7 2.7 XXX MNaOH (M) 0.5015 0.5015 XXX 0.09819 0.09819 XXX MNaOH (M) 0.5015 0.5015 XXX 0.09819 0.09819 XXX MNaOH (M) 0.5015 0.5015 XXX 0.09819 0.09819 XXX K Vsoln (ml) 5 5 5 4 4 4 Vsoln (ml) 10 10 10 4 4 4 Vsoln (ml) 10 10 10 4 4 4 Msoln (M) 0.737205 0.737205 0.737 0.638235 0.675056 0.657 Msoln (M) 0.351050 0.376125 0.364 0.176742 0.171833 0.174 Msoln (M) 0.174591 0.178675 0.177 0.066278 0.066278 0.066 n

Table 1. Initial concentration of Acetic Acid: 1.0M



 

Ether

Table 2. Initial concentration of Acetic Acid: 0.50M

Solvent water

Trial 1 2 Ave 1 2 Ave Trial 1 2 Ave 1 2 Ave

 

Ether

VI.

Discussion

Table 3. Initial concentration of Acetic Acid: 0.25M

Solvent water

The first part of the experiment was the standardization of the base, NaOH, which is to be used for the titration. The concentration of the base was determined by standardizing it with potassium hydrogen phthalate (KHP), MW=204.2 g/mol. KHP reacts with NaOH as shown in equation 1. KHP(aq) + NaOH(aq) NaKP(aq) + H20(liq) (Eq. 1)

Ether

Sample calculation for 0.10 M NaOH:  KHP x

 

Table 4. Values of K and n for the two concentration ranges

Concentration Range 0.5-1.0 M 0.25-0.5 M

 

= 0.097539 mol/L NaOH

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Afterwards, serial dilution was performed to prepare solutions of CH3COOH and NaOH separately with the following concentrations: 1.0 M, 0.5 M, and 0.25 M. To prepare 100 ml of 1.0 M solution from glacial acetic acid, which is 17.4 M, M1V1= M2V2 was used. Serial dilution is the stepwise dilution of a substance in solution. It is often employed to accurately produce highly diluted solution for experiments resulting in concentration curves with a logarithmic scale. Sample calculation for the volume of glacial acetic acid: M1V1= M2V2 V2 = 5.7471 ml Using a pipette, 5.75 ml of glacial acetic acid was obtained and diluted to the mark in 100-ml volumetric flask. Same procedure was done in the case of the other concentration. The main principle involved in this experiment is the Nernst distribution law. It states that at a given temperature, a substance will distribute itself between two immiscible solvents until at equilibrium the ratio of the activities of the substance in the two layers is constant. This behavior is a direct consequence of the thermodynamic requirements for equilibrium. To explain this, consider a pair of immiscible solvents in contact, A and B, both of which contain the same substance in the solution. The partial molar free energy of the solute in liquid A, A, can be represented by: A = A + RT ln aA (Eq 2)

ln (aB / aA) = constant and therefore, aB / aA = K (Eq 6) In more concentrated solutions, activities must be employed to obtain a true constant for the partition coefficient. When the solution is dilute or when it behaves ideally, the Nernst distribution law can be applied. The activity is essentially equal to the concentration C so equation 6 can be reduced to: CB/CA = K (Eq. 7) where K is the distribution or partition coefficient between the solvents which is the ratio of the concentrations of a compound in the two immiscible solvents at equilibrium. For the case of this experiment, the partition coefficient measures the differential solubility of acetic acid between water and diethyl ether. Some factors that may affect K are the nature of the solute and the solvents involved, concentration of the solute, temperature and the manner at which the constant is written. Like other equilibrium constant, partition coefficients also vary with temperature according to the equation: where is the difference in the free energy of the solute in the two layers. Although the partition coefficient is constant at constant T, its magnitude varies significantly as the temperature changes. However, the Nernst distribution law also has limitations such as its validity only when the solute undergoes no change such as association and dissociation. Acetic acid dissociates in water since it is a weak acid. Therefore, there is an + available H . If a solute, such as acetic acid, dissociates into ions or molecules or associates into more complex molecules, the Nernst distribution will no longer be applicable to the total concentrations in the two phases but only to the concentrations of the particular species common to both. The distribution law can only account for the activity of HOAc which is found in both aqueous and ether layers. For instance, 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:

while for the solute in liquid B, it can be shown as B = B + RT ln aB (Eq 3)

Since for equilibrium at constant temperature and pressure A = B, equations 2 and 3 becomes A + RT ln aA = B + RT ln aB (Eq 4)

and rearranging equation 4, it follows that A- B = RT ln aB - RT ln aA and ln (aB / aA) = (A- B)/RT (Eq 5) Since Aand B are constants at given temperature for a given substance in a particular solvent, equation 5 becomes Chem157.1, Distribution

where C2 is the concentration of the solute in the aqueous solution, C1 is the concentration of the solute in the organic solvent and n is the ratio of the Page 3 of 5

average molecular weight of the solute in solvent 1 to that in solvent 2. 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. Dissociation in water refers to the process of splitting or separation of the ionic compound intro smaller particles or ions plus the formation of hydronium. On the other hand, a hydrate is created when a substance associates with water to form a compound in which the water is present in its molecular form. Based on the results obtained in the experiment for both 1.0M and 0.5M concentrations, the values are greater than one which means that acetic acid dissociates in water forming a proton and acetate as its conjugate base. This is because water is a stronger base than acetate which means that it has a higher affinity for hydrogen ions than the conjugate base so hydrogen ions tend to leave the acetate and join the water to form a hydronium ion according to the following reaction: HC2H3O2(aq) + H2O(l) =>H3O
+ (aq)+C2H3O2(aq)

VIII.

References

Maron, H, Lando, J. (1974). Fundamentals of Physical Chemistry, pp 465-468. Satake, M., Nagahiro, T.(1990). Modern dictionary: physical chemistry. New Delhi: Discovery Publishing House. Standardizing a Sodium Hydroxide solution. Retrieved Jan. 26, 2011 from http://www.cerlabs.com/experiments/10875 406181.pdf I hereby certify that I have given substantial contribution to this report.

Jessica Marie Velasquez Montes

The method used to measure the concentration of the solute in each solvent is the Shake flask/tube method. It is consists of dissolving some of the solute in question in a volume of two immiscible liquids. So far, this method has been the most accurate and it can be used in broad ranges of solutes. Titration of the two solvents with a standard base was employed to determine the concentration of the solute in each of the solvents using the formula M1V1=M2V2. VII. Conclusions and Recommendations

Maiko Luz Villanueva Dulos

. From the experiment performed, it was calculated that the K and n values in the concentration range 0.50 M-1.0 M are 0.8567 and 1.8834 while for the 0.25 M- 0.50 M, they are 1.4769 and 1.3345 respectively. Since n>1, acetic acid dissociates in water. The Nernst distribution law can be applied in experiments involving extraction, determination of equilibrium constants, and analysis. It permits experimenters to determine the most favourable conditions for the extraction of substances from solutions. However, it is only valid when the solutions are ideal and dilute, the presence of solute does not change the mutual solubility of the two layers, and the solute has the same molecular mass in both layers. Chem157.1, Distribution Page 4 of 5

Answers to guide questions: 1. Does acetic acid dissociate or associate in water? Why? Based on the results obtained in the experiment for both 1.0M and 0.5M concentrations, the values of n were greater than one which means that acetic acid dissociates in water forming a proton and acetate as its conjugate base. This is because water is a stronger base than acetate which means that it has a higher affinity for hydrogen ions that the conjugate base so hydrogen ions tend to leave the acetate and join the water to form a hydronium ion.

2. How does dilution affect dissociation or association of acetic acid in water? Explain. Dilution increases the value of n of the acetic acid so acetic acid dissociates in water. This is due to the fact that the solute-solvent interaction becomes greater than solute-solute interaction after dilution.

Chem157.1, Distribution

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