ADAMSON UNIVERSITY

College of Engineering
Chemical Engineering Department
M a n il a

EXPERIMENT NO. 4

DISTRIBUTION

Aguilar, Vanessa Denise C.

Section: 51018

Schedule: Friday, 10:30-1:30, OZ 403

BS Chemical Engineering, 3rd year

Date performed:January 29, 2016

Date submitted: February 5, 2016

ABSTRACT:

The distribution constant is used in determining the amount of solute in two solvents when a solute is added

to solvents mixed. This experiment determined the value of K in the distribution of acetic acid between water and

ether. Various concentrations of acetic acid in water and ether are prepared and the concentrations of the mixtures

are found by titration with NaOH. The resulting concentrations were computed and used in the calculation of K and

n. Results showed that the value of n in the concentration range of 0.50-1.0M is greater than 1, thus acetic acid

dissociates in water. The average molecular weight of the acetic acid was decreased due to the dissociation. This

experiment successfully determined the distribution constant of acetic acid in water and ether. The method in this

experiment can also be applied to other ternary system where a solute is added to two immiscible solvents.

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-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.

In mixtures, when two solvents are mixed in a binary system and a solute is added, the

amount of solute in two solvents can be determined by using the distribution constant. The
relations involving the distribution constant and the activities of the solute in two solvents is

given by the equation:

an2
Ka=
a1

Kais the distribution constant and a1 and a1 are referring to activities of the solute in two

solvents, and n is computed by

mw of solvent 1
n=
mw of solvent 2

The average molecular weight is affected by the degrees of association and dissociation.

The values of n also changes with concentrations.

If concentration is used instead of activities, the relationships for the distribution

constant becomes

C n2
K c=
C1

This experiment determined the values of K and n in the distribution of acetic acid

between water and ether. The K and n for the ternary system was calculated after doing the

experiment getting the data required.

REVIEW OF RELATED LITERATURE:

Distribution law (Martin, 2012) or the Nernst's distribution law gives a generalization

which governs the distribution of a solute between two non-miscible solvents. This law was first

given by Nernst who studied the distribution of several solutes between different appropriate

pairs of solvents.The statement of the law is"If a solute X distributes itself between two non-

miscible solvents A & B at constant temperature & X is in the same molecular condition in both

the solvents, then: concentration of X in A / Concentration of X in B = K d"Where Kd is called

the distribution coefficient or the partition coefficient.If C1 denotes

the concentration of solute in solvent A & C2, the concentration of X in B; Nernst's distribution

law can be expressed as C1/C2 = Kd(Athawale, 2006)

Two immiscible liquids are connected to each other through the boundary surface

between them. These liquids are called phases. If one of these phases also contains a third

substance A, a part of that substance will be transferred into the phase where its chemical

potential is lower, until substance A’s chemical potential in both phases is the same. (Fegley,

2013) In practice, one can put in a separatory funnel two immiscible liquids like water and

diethyl ether. The water also contains acetic acid, making the water phase in fact a liquid solution

of acetic acid. (Mathur, 2006)

When a solute is shaken with two non-miscible solvents, at equilibrium both the solvents

are saturated with the solute. Since the solubility also represents concentration, we can write the

distribution law.Hence knowing the value of the Distribution coefficient (KD) and the solubility

of solute in one of the solvents, the solubility of solute in the second solvent can be calculated.

(Macias et. al, 2001)

 The conditions to be satisfied for the application of the Nernst’s Distribution law are

constant temperature. The temperature is kept constant throughout the experiment.(Choppin,

2000) Same molecular state the molecular state of the solute is the same in the two solvents. The

law does not hold if there is association or dissociation of the solute in one of the solvents.

Equilibrium concentrations the concentrations of the solute are noted after the equilibriumhas

been established. (Cox, 2002) Dilute solutions the concentration of the solute in the two solvents

is low. The law doesnot hold when the concentrations are high. Non-miscibility of solvents the

two solvents are non-miscible or only slightly soluble ineach other. The extent of mutual

solubility of the solvents remains unaltered by the addition of solute to them. (Rydberg, 2002)

It was pointed out by Nernst that C1/C2 is constant only if the solute exists as simple

moleculesin the two solvents. If the solute undergoes association or dissociation in one of the

solvents, it is found that C1/C2 is not constant. In these cases, distribution law applies only to

that part of the solute which is present as simple molecules. (Kislik, 2012)

The Nernst distribution law, which is used by many authors in geology as the theoretical

basis of geothermometry and trace-component distribution, is derived using excess functions' It

is demonstrated that the free-energy term in the Nernst equation, as it is applied in many of these

cases, is an excess function and describes the non-ideal behavior of the phases involved. It is

then not necessary to introduce any assumptions concerning activities or activity coefficients,

and one may use simple mole fractions instead. (Holst, 2008)

The derivation ofthe Nernst equation is dependent on the convention one uses for dealing

with non-ideality in solutions. There are two common conventions: activities, and

thermodynamic excess functions. There are two systems of activities (Castellan, 2001) the
rational system using Raoult's law as thelimiting case (activity coefficient approaches I as mole

fraction approaches I and the practical systemusing Henry's law as the limiting case (activity

coefficient approaches I as mole fraction approaches 0. Activities are more commonly used in

geological literature,but excess functions would be more effective and eliminate confusion in

some instances. A more complete discussion of thermodynamic excess functions can be found in

(Thompson, 2007) or (Swalin, 2002).

Methodology:

1.0M and 0.50M of glacial acetic acid were prepared using the calculated volumes thru

the dilution equation, of acetic acid and water needed to prepare the desired solution.

0.5M NaOH was prepared from 20 grams of NaOH pellets diluted in 1L of water, the

resulting solution served as the titrant. 25ml of the 1M glacial acetic solution was pipetted into a

separatory funnel then, 25ml of diethyl ether was added. The mixture was shaken well, and the

pressure was released using the stopcock. The layers completely separated after standing for 10

minutes.

The aqueous layer (bottom layer) was drawn from the separatory funnel. 5.0ml of the

aqueous layer was pipetted into a clean 125ml Erlenmeyer flask and 10ml of distilled water was

added. The solution was titrated with 0.5M NaOH to the faint pink phenolphthalein end point.

Two trials were made.

The remaining ether layer was drawn from the separatory funnel. 10ml of the ether layer

was pipetted into a 125 ml Erlenmeyer flask, and 10ml of distilled water was added. The solution
was titrated with 0.5M NaOH to the faint pink phenolphthalein end point. Two trials were made

as well.

Repeat the previous steps using 0.5M of glacial acetic acid. Calculate the concentration

of the acetic acid in each solution.

Finally, determine the values of K and n for the concentration used.

RESULTS:

A. INITIAL CONCENTRATION OF ACETIC ACID: 1.0 M

Solvent Trial VNaOH MNaOH Vsolution Msolution

1 5.60ml 0.5 15ml 0.187M

2 5.65ml 0.5 15ml 0.188M

WATER

Average 0.188M

1 3.80ml 0.5 20ml 0.095M

ETHER 2 4.25ml 0.5 20ml 0.106M

0.101M
Average

B. INITIAL CONCENTRATION OF ACETIC ACID: 0.5 M

Solvent Trial VNaOH MNaOH Vsolution Msolution

1 2.85ml 0.5 15ml 0.0950

WATER 2 2.85ml 0.5 15ml 0.0950

 Average 0.0950

1 1.9ml 0.5 20ml 0.0475

ETHER 2 2.0ml 0.5 20ml 0.0500

0.0488
Average

Value of K and n in concentration range

Concentration Range K n
0.50 – 1.0M 1.67 1.066

DISCUSSION OF RESULTS:

The results showed the different concentrations of the solute in the two solvents. The

value of K and n was computed for the range of 0.50-1.0M. The computation of K and n

involved the substitution of the values of concentrations that were gathered from titration. The

value of K and n for 0.5-1.0M range is 1.67 and 1.066 respectively.

The acetic acid, which is the solute, dissociates in water since it is a weak acid. The

dissociation follows the equation:

+ ¿¿

H C2 H 3 O2 →C 2 H 3 O 2−¿+H ¿

The acetic acid dissociates into acetate and hydrogen ion. Acetic acid is a weak acid, and

thus a weak electrolyte. Weak electrolytes are not 100% ionized in water.
 Since the acetic acid dissociates in water, the average molecular weight of the acetic acid

is decreased due to the dissociation.

According to table A, the average molarity in water solvent is 0.188M, whereas in the

ether solvent is 0.101M, which is lower than that of the water solvent. In table B, the average

molarity in water solvent is 0.0950 while in 0.0488 in ether solvent. The volumes of NaOH that

was from titration in both 1.0M and 0.50M solute concentration are greater than in water solvent

that in the ether solvent.

The data showed in both initial concentrations of acetic acid that the molarity of the

solution is higher when it is in water solvent, and lower when it is in ether solvent. This

phenomenon is due to that the distribution coefficient which is 1.67 implies that the solute is

more soluble in water than in ether, since it is greater than one. The distribution law is also

associated with the solubility of the solute in solvent (Castellan, 1971).

The dilution of acetic acid increases the dissociation constant of the acetic acid.This is

based on Ostwald’s dilution law which states that for a weak electrolyte the degree of ionization

is inversely proportional to the square root of molar concentration of the solute. As the molarity

decreases for a weak electrolyte like acetic acid, the dilution or dissociation constant increases.

The possible sources of error are personal and instrumental errors. The burette pipe that

was used in the experiment has a leak problem, and the tip of the burette was loosened, resulting

in the inaccurate volume reading. Few air bubbles were also present in the burette pipe. The

experimenters were unable to use the half drop method during the titration process of some

mixtures thus resulting in the dark pink end point of the solution.
CONCLUSION AND RECOMMENDATION:

The experimenters were able to determine the values of dissociation constant of

the acetic acid in the ether-water system.Since n is greater than 1, acetic acid dissociates in

water. The average molecular weight of the acetic acid was decreased due to the dissociation.

The solute which is acetic acid distributed itself between the two immiscible solvents which are

water and ether at constant temperature and the solute is in the same molecular condition in both

solvents. The concentration of acetic acid is greater than in water solvent, resulting in the K

value of 1.67.

The experimenters recommend the frequent checking of the burette pipe for leak

problems. To assure accuracy of volume reading, standardization of titrant which is NaOH, must

be done before titrating the solutions, by the use of KHP (Potassium Hydrogen Phthalate). Half

drop method must always be observed in the titration procedure to obtain the correct transition

range, resulting in faint pink color, of the phenolphthalein indicator. The experimenters also

recommend using the method in this experiment to determine the distribution constant of other

important ternary system.

REFERENCES:

Broecker, W.S. and V. M. Oversby (1971) Chemical Equilibria in the Earth, McGraw-Hill Book
Co., New York.

BrucceFegley, Jr. (2013) with distributions by Rose Osborne, Practical Chemical

Thermodynamics for Geoscientist, pp. 371-377

Castellan, G. W. (1971) Physical Chemistry.Addison-Wesley Publishing Co., Reading, Mass.

Jan Rydberg, Michael Cox, Claude Musikas, Gregory R. Choppim (2002), Solvent Extraction
Principles and Practice, second edition, revised and expanded, pp. 109-202

Lindsley, D. H. and S. A Dixon (2006) Diopside-enstatiteequilibriaat 850"C to 1400'C,5 to 35

kbar. Am. J.Sci.,276, 1285-130

Macias, M., Ildefonso, C., Cantero, D. (2001) Chemical Engineering Journal, Vol. 65. pp. 201-
207.

Martin's Physical Pharmacy & pharmaceutical sciences; fifth edition (2012), Patrick.J.Sinko,
Lippincotwilliams&wilkins.

Norman B. Holst, Jr. (2008) the use of thermodynamic excess functions in the Nernst
distribution law, American Mineralogist, Volume 63, pp. 83-86, 2008

Swalin, R. A. (2002) Thermodynamics of Solids. John Wiley and Sons, New York.

V.D Arthawale, Paul Marthur (2006) Experimental Physical Chemistry, New Age International
Limited Publishers, Nernst Distribution Law pp. 25-31

Vladimir S. Kislik (2012), Solvent Extraction: Classical and Novel Approaches, pp. 55-58
APPENDIX:
SAMPLE CALCULATIONS:

NaOH (aq)+ H C 2 H 3 O 2(aq) → Na +¿ −¿

(aq) +C 2 H 3 O 2( aq ) + H 2 O ( L ) ¿ ¿

molesNaOH = moles acetic acid

moles acetic acid=M NaOH V NaOH

moles acetic acid =( 0.5 M ) ( 5.60 x 10−3 L )=2.8 x 10−3 moles

moles acetic acid

Molarity soln=
liter of sol ' n

2.8 x 10−3 moles

Molarity soln= =0.187 M
0.015 L

Solving for K and n:

For 0.5 M

C 2n
K=
C1

(0.095)n
K=
(0.0488)

For 1.0 M

(0.188)n
K=
(0.101)

Solving for n, equate the two equations:

 (0.095)n (0.188)n
→ =
(0.0488) 0.101

(0.095)n (0.0488)
→ =
(0.188)n 0.101

0.095n 0.0488
→ log ⁡ n
=log
0.188 0.101

0.0488
n log 0.095−n log 0.188=log
0.101

n¿

n=1.066

Substituting n∈both k equations :

(0.095)1.066 (0.188)1.066
=
(0.0488) 0.101

1.67=1.67

k =1.67