Distribution of a Solute between Immiscible Solvents

V.O.L.Tabell
Department of Mining, Metallurgical and Materials Engineering
University of the Philippines, Diliman
vo_tabell@yahoo.com
Abstract
This paper discusses the significance of determining the distribution of a solute between
immiscible solvents. Using water and diethyl ether as solvents and acetic acid as the solute,
the experiment showed the effects of the varying concentrations of the solute to the
distribution coefficient of the mixture. Titration using NaOH to compute the concentration of
HOAc in the mixture showed results that sufficiently explained the theoretical equations
formulated prior to the experiment. Although there were some errors as seen in the
distribution coefficient computed from the 2.0N solution and in the computed n value from the
logarithmic plot of the solute concentrations, which was inferred to be due to over titration.
Moreover, the experiment introduces the concept behind the extraction technique used in
many fields in the industry today.

1. Introduction
Studies are made of the equilibrium distributions
of a solute between two immiscible solvents
because such experiments give evidence of
association or dissociation of the solute in one of
the phases [1].
The extraction technique is based on the fact that
if a substance is insoluble to some extent in two
immiscible liquids, it can be transferred from one
liquid to the other by shaking it together with the
two liquids [2]. When two liquid phases are in
equilibrium with each other, a dissolved substance
will distribute itself between the two according to a
definite equilibrium [1].
This provides information as to the nature of
complex ions and their dissociation constants.

KC

Ci
Ci

(Equation 1)

If it is assumed, on the other hand, that the solute

is associated to form an n-mer in the organic or
phase, the distribution coefficient will follow the
equation:

KC

C i

(Equation 2)

If the association is complete, the n value is an

integer; however if the association is incomplete,
the n value will not be an integer and may vary
with concentration.

In line with this, a method called fractional

separation is applied for the analysis of the two
distinct phases or immiscible liquids.

This experiment aims to look into the effects

produced by the distribution coefficient as well as
the concentration of the solute in both solvents,
because such data are of value in the design and
operation of solvent-extraction equipments.

The ratio of the concentration of the solute in

each solvent at equilibrium is a constant called the
distribution coefficient (Kc).

2. Methodology

If it is assumed that the activity coefficients of

both

and

phases, being yi and yi , are

concentration dependent then the distribution

coefficient of the of the solute follows the equation:

Acetic acid in water was prepared in 0.5N, 1.0N

and 2.0N concentrations, and 25mL of each
solution was pipetted into three closed 100mL
separatory funnels. Then, 25mL of diethyl ether
was added to each funnel and were set in a

Tabell, Victor Oliver. Distribution of a Solute between Immiscible Solvents. Page 1 of 4

thermostat of 25C with frequent shaking for 20

minutes.

2.0N
Water

1.92M HOAc

diethyl ether

1.275M HOAc

From here on, the aqueous and ether phases of

the mixture will be assigned as and phases,
respectively.
If it is assumed that the activity coefficients of
both
Figure 1. Experiment Setup [3]
After shaking, the funnels were opened to
separate the lower layer of the mixture into
Erlenmeyer flasks. The upper layer left in the
funnels was pipetted into separate Erlenmeyer
flasks, thereby producing six flasks ready for
titration of 0.5N NaOH.
Using phenolphthalein as an indicator, the ether
solutions and the aqueous solutions, 10mL per flask,
were titrated until the solution turned faint pink in
color. The amounts of NaOH used for each flask
were recorded for further analysis.

3. Results and Discussion

The amounts of NaOH used in the titration
process were recorded in order to determine the
concentrations of HOAc in the aqueous and ether
solutions. Using the reaction equation between
sodium hydroxide and acetic acid in standard room
temperature:

HOAc + NaOH NaOAc + H2O

It is evident that the molar ratio of OAc- to Na+ is
equal to 1. Knowing the concentration and amount
of NaOH used together with the initial amount of
solution which is 10mL, dimensional analysis
would yield the concentration value of HOAc in
each solution. These values are tabulated in Table 1.
Table 1. Computed Concentrations
0.5N

and

phases, being yi and yi , are

concentration dependent then the distribution

coefficient of the of the HOAc solute follows
Equation 1. The computed values for Kc are shown
in Table 2.
Table 2. Computed K values
K values
0.5N

0.28933

1.0N

0.28992

2.0N

0.664063

From the table, we notice the similar values of K c

for the 0.5N and 1.0N concentrations and a
somewhat different value for the 2.0N
concentration. Normally, if more of the solute is
added to the system, it will redistribute itself
between the immiscible liquids so that the ratio of
the solute concentrations remains the same, hence
maintaining the same value of Kc [4]. For the case
of the 2.0N of HOAc, it could be inferred that a
primary reason for the deviated value of Kc was
over titration. It could be that because of an over
titrated ether solution, there was an increase in the
amount of NaOH used, hence increasing the
expected Kc value from around 0.289 to 0.664.
If it is assumed, on the other hand, that the the
HOAc solute is associated to form an n-mer in the
organic or phase, the distribution coefficient
will follow Equation 2.

Water

1.3825M HOAc

diethyl ether

0.4M HOAc

To solve for the value of n from Equation 2,

assuming the occurrence mentioned, the equation
for the distribution coefficient can be manipulated
to create the linear expression:

Water

2.36M HOAc

n[log( Ci )] = log( Ci ) log( K C )

diethyl ether

0.6825M HOAc

1.0N

Tabell, Victor Oliver. Distribution of a Solute between Immiscible Solvents. Page 2 of 4

with log( Ci ) and log( Ci ) being the x and y

variables respectively, and n as the slope. Table 3

tabulates the values of both log( Ci ) and log( Ci ),

and Figure 2 illustrates the graph with a linear trend
line.
Table 3. Logarithmic values of Solute
Concentration
Concentration

log( Ci )

log( Ci )

0.5N

0.140665

-0.39794

1.0N

0.372912

-0.1659

2.0N

0.283301

0.10551

Considering the conditions mentioned in the

experiment, the value of the distribution coefficient
can be determined. With such values obtainable
through experiment, the design and operation of
solvent-extraction equipments are made possible.
There are numerous practical applications for
the concept of extraction. One in particular is
testing the absorption of harmful chemicals or
pesticides by fatty tissue [4]. The idea for this is
that the pesticide molecules must be much more
soluble in the very weakly or non-polar fat-'solvent'
than in water. This case study originated from the
dilemma that herbivorous animals in the ecosystem
take in large concentrations of pesticide present in
crops which in turn creates instability in the food
chain because of unaccounted deaths. With the
technique of extraction, the concentration of
pesticide can be measured and modulated when
applied to crops.

4. Conclusion

Figure 2. *log(A) is log( Ci ) and log(B) is log( Ci )

From the slope of the trend line formed from the
graph, the n value was found to be 1.2316. The n
value not being an integer suggests that if, in the
assumption that the solute forms an n-mer with
the phase, the association of the solute is not
complete. One probable reason for the
incompleteness of the association of the solute to
the solvents is the improper shaking during the part
when both solvents were inside the separatory
funnel. It could be that the shaking wasnt done
diligently enough for the solute to distribute itself
within the solvent. The n value being that close to
unity could mean that there was only a relatively
small error in the logarithmic values of the solvent
concentrations. On another note, this could also be
due to the concentration of the HOAc solute in the
mixture [1].

3.2 Other Discussions

Extraction is a convenient method for separating
an organic substance from a mixture [4]. From the
experiment, it can be determined if the solute used
in the two solvents dissociates completely or not.

The experiment showed the effects of the varying

concentrations of the solute to the distribution
coefficient of the mixture. Titration using NaOH to
compute the concentration of HOAc in the mixture
showed results that sufficiently explained the
theoretical equations formulated prior to the
experiment. Although there were some errors in the
experiment, as seen in the distribution coefficient
computed from the 2.0N solution and in the
computed n value from the logarithmic plot of the
solute concentrations, much was learned from this
experiment.
The study of the distribution of the solute in
immiscible solvents gave way to the establishment
of the extraction technique used in many fields in
the industry.

References
[1] "Distribution of a Solute between Immiscible
Solvents." Metallurgical
Engineering
18
Laboratory Manual. (2012)
[2] Pahlavan, . "Determination of Distribution
Coefficient." . N.p.. Web. 17 Dec 2012.
<https://docs.google.com/viewer?a=v&q=cache:H
XenU70L_50J:swc2.hccs.edu/pahlavan/>.
[3] Lamanilao, Juphil. "Distribution of a Solute
between Immiscible Solvents." . N.p.. Web. 17 Dec
2012.
<http://www.slideshare.net/jeufier/distribution-ofa-solute-between-immiscible-solvents>.

Tabell, Victor Oliver. Distribution of a Solute between Immiscible Solvents. Page 3 of 4

[4] "Partition equilibrium between two phases,

partition coefficient, immiscible liquids and solvent
extraction."Doc Brown. N.p.. Web. 18 Dec 2012.
<http://www.docbrown.info/page07/equilibria4.ht
m>.

Appendix
Sample Calculations
i.

Concentration of Solute(HOAc)

C = (27.65mL NaOH) x
(0.5mmol NaOH/ mL NaOH) x
(1mmol HOAc/1mmol NaOH) x
(1/ 10mL HOAc)
C = 1.3825 M HOAc
ii.

Distribution Coefficient

KC

Ci
Ci

Kc = 0.4M / 1.3825M
Kc = 0.28933

Tabell, Victor Oliver. Distribution of a Solute between Immiscible Solvents. Page 4 of 4