OBJECTIVES

0 With this practice the student will understand

the physicochemical phenomena of the
distribution of ionization and dimerization of the
benzoic acid that is carried out in two phases
(benzene and water), as well as the equilibrium
conditions towards the product that one wishes
to obtain in greater quantity.
THEORETICAL CONCEPTS
0 The non-ideal behavior of the solutions is
explained in terms of intermolecular physical
forces.

Note: However, there are other intermolecular

forces that act on different molecules or ions that
cause them to attract or repel each other. These
forces determine the physical properties of
substances, such as, for example, the state of
aggregation, the melting and boiling point,
solubility, surface tension, density, etc.
 BUT NEVERTHELESS...
0 "The molecules in a liquid solution interact with
others in such a direction that they form new
chemical species, so the non-ideality of the solution
is a consequence of the chemical reactions”.

Knowing this we can talk about two types of

reactions

0 Association
0 Solvation
 ASSOCIATION
0 It is the formation of chemical aggregates as
polymers from identical monomers.

Note: Polymerization is a chemical process by

which reagents, monomers are chemically
grouped together.
 DIMERIZATION
0 It is a common case of the association.

0 And the dimerization is defined as two identical

molecules join to form a new molecule that is
just twice the other two.

0 The chemical structure formed by the

dimerization is called dimer.
 SOLVATATION
0 It refers to the formation of chemical aggregates of
two or more molecules of which at least two are
identical.

0 The dimerization and solvation are due to hydrogen

bridges.

0 Note: The force by hydrogen bond or hydrogen

bond is the eminently electrostatic force attractive
between an electronegative atom and a hydrogen
atom covalently bound to another electronegative
atom.
 SOME CONCEPTS
PREVIOUS AMOUNTS
0 Solution: It is a homogeneous mixture of two or more
substances. The dissolved substance is called a
solute and the substance where it is dissolved is
called a solvent or solvent.

0 Partition coefficient (P), is the quotient or ratio

between the concentrations of that substance in
the two phases of the mixture formed by two
immiscible solvents in equilibrium.

0 Immiscible: That can not be mixed.

 DISTRIBUTION OF ONE SOLUTION
AMONG TWO IMMISSIABLE
SOLVENTS
 Consider two liquid phases a and b; Like a solute (1)
distributed between two phases, however, its mole
fraction of this solute is so small that we can assume
ideal behavior of the solutions.

0 Henry's Law has to do with the principles related to

dissolved gas and pressure. It establishes that the
amount of gas dissolved in equilibrium in a certain
volume of liquid is directly proportional to the
pressure of the gas that makes contact with the
surface of the liquid.
When the two phases are in equilibrium, the
fugacity of the substances in both phases is the
same. For which we can say that ...

Since the mole fraction of a and b are very

small then the concentrations of the solute in
both phases are proportional and since the
mole fraction is very small we have the densities
of the pure solvents.
The Nernst distribution law
0 The Law of distribution of Nernst or law of
distribution, is defined when a substance is
distributed between two liquids miscible to
each other or slightly miscible, and the ratio of
the concentrations of said substance in the two
phases is constant, regardless of the amount of
solute dissolves or the volume of liquid used.

0 This law was raised by Walther Nernst in 1931.

In its more general statement it states that when a
certain amount of solute is distributed between two
immiscible solvents, a state of equilibrium is reached in
which both the chemical potential and the transience
of the solute is the same in the two phases.
Therefore, if we consider two solvents «A» and «B» that
form two separate phases when they are in contact
and we assume that a small amount of solute «i»
dissolves in both phases forming two ideal equilibrium
solutions, the quotient of molar fractions of the solute in
the two phases can be expressed well

0 x=mole fraction of the solute in each solvent

0 µ= fugacity
0 N= distribution coefficient
On the other hand, if the solutions are sufficiently
diluted, this coefficient can be found from the
constants of Henry's law for "i" in the solvents "A"
and "B", symbolized by kH.

In the ideal case in which the activities (a) of the

solute in both phases are very similar, so we can
suppose them equivalent to the concentrations c,
we arrive at a single constant K, which as we have
seen, depends on the temperature and the
Pressure.
 LIMITATIONS
0 The law is strictly valid for diluted solutions.

0 If one of the solvents is saturated is solute, it can not

undoubtedly dissolve more mass of said solute, so
that if the other solvent is not saturated, the
relationship between the concentrations will not be
constant.

0 If the solute is associated or dissociated in one

solvent and is not in the other, that is, it does not
have the mass-formula corresponding to a simple
structure in both solvents, the relationship between
the concentrations will not be constant
 EXPERIMENTAL
DEVELOPMEN
0 Prepare a solution of 4-5 gr / L of benzoic acid solution in benzene.

0 Place different mL samples of this solution in separation funnels.

0 Add 25 mL of water to each funnel and enough benzene to obtain

50 mL.

0 Shake and let stand for 30 minutes to reach equilibrium.

0 Take 10 mL aliquot of each phase.

0 Titrate with 0.015N NaOH and with phenoftalein.

Note: for the titration of the organic phase add water.

 CALCULATIONS AND RESULT
0 1.- Balance of acid distribution

𝐻𝐵𝑧 𝑏
𝐾𝐷 =
𝐻𝐵𝑧 𝑎
0 2.- Chemical equilibrium in aqueous phase

𝐾𝑎
Acid (not ionized) in wáter 𝐻 + + 𝐵𝑧 −

0 3.- Dimerization constant

(𝐻𝐵𝑧) 2 𝑏
𝐾𝑀 =
𝐻𝐵𝑧 ∧ 2𝑏
 Developing a balance for each pase. CA for
aqueous phase and CB for organic phase. The
following expressions are obtained.

1.- 𝐶𝐴 = 𝐻𝐵𝑧 𝑎 + 𝐵𝑧 = 𝐶𝐴 1 − 𝛼 + 𝐶𝐴 𝛼

2.- 𝐶𝐵 = 𝐻𝐵𝑧 𝑏 + 2 (𝐻𝐵𝑧)2 𝑏

𝐶𝐵
3.- = 𝐾𝐷 + 2𝐾 2 𝐷 + 𝐾𝑀 𝐶𝐴 1 − 𝛼
𝐶𝐴 (1−𝛼)

𝛼 2 𝐶𝐴
4.- 𝐾𝐴 =
1−𝛼
 From the results obtained in the titration.
The molar concentrations of the benzoic acid
can be obtained in each phase

𝑉𝐴 𝑁𝑁𝑎𝑂𝐻
01.- 𝐶𝐴 =
𝑉𝑚

𝑉𝐵 𝑁𝑁𝑎𝑂𝐻
02.- 𝐶𝐵 =
𝑉𝑚
 RESULTS
0 From other practices analyzed the following
results were obtained
Sistema 1 2 3 4 5

CA 0.0314 0.0246 0.0167 0.01069 0.0064

CB 0.0047 0.0036 0.0043 0.0034 0.0031

Km 6.59 6.83 3.82 3.110 2.0705

α 0.11326 0.1283 0.1180 0.13177 0.1375

y 7.4360 7.8390 4.3358 3.6069 2.4006

x 0.0042 0.0031 0.0038 0.0029 0.0026

Kd 35.5380 33.0843 105.7639 159.5672 360.0095

 y
8
y = 3086.7x - 5.4992
R² = 0.9971
7

4 y
Linear (y)

0
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035 0.004 0.0045
OBTENCIÓN DE DEHIDRODIISOEUGENOL POR DIMERIZACIÓN DE
ISOEUGENOL CON CULTIVOS CELULARES DE Bouvardia ternifolia
(TROMPETILLA)Dehidrodiisoeugenol by dimerization of
isoeugenol with cell culture of Bouvardia ternifolia

0 Cell cultures of Bouvardia ternifolia were used as catalyst

for the oxidative coupling of isoeugenol, to produce
dehydrodiisoeugenol, a dimer, 77% isolated yield, when
using the supernatat from the cell cultures suspension
having peroxidase activity. The biotransformation
proceeded under very mild conditions. It was observed
that an increase in the amount of hydrogen peroxide
decreases the yield.