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:

K a=

a n2
a1

Ka is the distribution constant and a1 and a1 are referring to activities of the solute in two
solvents, and n is computed by

n=

mw of solvent 1
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
n

K c=

C2
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 nonmiscible 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 As 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 Nernsts 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 equilibrium has
been established. (Cox, 2002) Dilute solutions the concentration of the solute in the two solvents
is low. The law does not hold when the concentrations are high. Non-miscibility of solvents the
two solvents are non-miscible or only slightly soluble in each 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
molecules in 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 of the 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 the limiting case (activity coefficient approaches I as mole
fraction approaches I and the practical system using 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

5.60ml

0.5

15ml

0.187M

5.65ml

0.5

15ml

0.188M

WATER

0.188M

Average

ETHER

3.80ml

0.5

20ml

0.095M

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

WATER

2.85ml

0.5

15ml

0.0950

2.85ml

0.5

15ml

0.0950
0.0950

Average

ETHER

1.9ml

0.5

20ml

0.0475

2.0ml

0.5

20ml

0.0500
0.0488

Average

Value of K and n in concentration range

Concentration Range

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
H C 2 H 3 O 2 C 2 H 3 O 2

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 Ostwalds 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.
Brucce Fegley, 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-enstatite equilibria at 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. 201207.

Martin's Physical Pharmacy & pharmaceutical sciences; fifth edition (2012), Patrick.J.Sinko,
Lippincot williams & 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:
C2 H 3 O2
( aq ) + H 2 O ( L )
+
Na(aq)+
NaOH (aq )+H C 2 H 3 O2(aq)

moles NaOH = moles acetic acid

moles acetic acid=M NaOH V NaOH
moles acetic acid=( 0.5 M ) ( 5.60 x 103 L )=2.8 x 103 moles

Molarity soln=

Molarity soln=

moles acetic acid

liter of sol ' n

2.8 x 103 moles

=0.187 M
0.015 L

Solving for K and n:

For 0.5 M

C 2n
K=
C1

(0.095)
K=
( 0.0488)
For 1.0 M

K=

(0.188)n
(0.101)

Solving for n, equate the two equations:

n

(0.095) ( 0.188)

=
(0.0488)
0.101

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

0.095 n
0.0488
log
=log
n
0.101
0.188

n log 0.095n log 0.188=log

0.0488
0.101

0.188
log 0.095log =log
n
n=1.066

Substituting nbothk equations :

0.0488
0.101

1.066

1.066

(0.095)
(0.188)
=
(0.0488)
0.101

1.67=1.67

k =1.67