Fundamentals of Distribution Separations (II)

(01/12/15)

1. Principles of distribution equilibria

dG = -S * dT + V* dP +

int
(i +

ext
i )dni (open systems under external

field)

-i - i ext
K = exp
RT
-0
-0
i = Hi TSi
0

distribution coefficient

A---B

2. Intermolecular interactions

A + B

Intermolecular Interactions
Intermolecular interactions:
Dissociation of H2O = 200 kcal/mol (H2O
2 H + O)
Vaporization energy of H2O = 9.7 kcal/mol (H2Ol
H2Og )
Intermolecular interactions are weaker than intramolecular interactions, but
It is determining solubility, boiling points, vapor pressure, melting points.
These properties are of importance in determining the behavior of
compound in chromatography and other separation methods
A useful general principle in separation is like dissolves like. In other words,
a molecule will interaction most strongly with the phase or solvent that is most
similar to it in its chemical characters.
Question:

glucose (1)
naphthalene (2)

Hexane (1)
Water (2)

Intermolecular Interactions
The intermolecular interactions can either be attactive or repulsive in nature.
r
i

j
Etotal = A/r12 B/rz
Where: E total = net total energy of interactions
A = constant describing repulsive forces between i and j
B = constant describing attractive forces between i and j
z = constant for a given type of attractive force
Lennard-Jones potential: z=6
1. Dipole-dipole interaction
2. Induction interaction
3. Dispersion interaction (London forces)
4. Hydrogen bond

van der Waals forces

Electrostatic interaction (Coulombic)

(hard interactions)
5. Lewis acid-base interactions
Electron transfer (sharing electron)
(soft interactions)

1. Dipole-dipole interaction
+
-

j
2

ED = -

+
j

i j

3 (4 0)2 kTr6

i, j = dipole moments of i and j

T = Temperature
k = Boltzmanns constant
Note: Temperature dependent

2. Induction interaction

+
i

+
i

j
2

EI = -

i j
(4 0)2 r6

i = dipole moments of i
j = polarizability of j
Note: independent of temperature

+
j

3. Dispersion interactions (London Force)

i
EL = -

j
3 h i j

+
j

two atoms

4 (4 0)2 r6
i, j = polarizability of i and j

r = distance
h = Planks constant
= Frequency of light required for ionization of each species
0 = dielectric permittivity of the medium
EL = -CL Vi (i)v (j)v two molecules
(i)v (j)v = polarizability of i (solute) and j (solvent) per unit volume
CL: Dispersion constant (uniform for most compounds)
Vi = Molar volume of i (MW/density)

4. Hydrogen bonds
Non-covalent bond forms between a molecule with a proton donor group
And proton acceptor group.
(a) Common proton donors are OH, -NH, and SH
(b) Common proton acceptor are O-, =N-, -F, -S-, -Cl, C=C..
(c) E ~ 1/r6
(d) Hydrogen bond is one example of a more general class of Lewis
acid-base interactions.
A + :B

A:B

5. Lewis acid-base interactions

(A) Electrostatic interaction (Coulombic)
(hard interactions)

(1) Coulombic interaction

EAB =

QiQj

Gilbert N. Lewis

4 0 r

(2) Interactions with polar and non-ionic compounds (ED)

2

ED = -

Qi j

6 (4 0)2 kTr4

i
+

polar

(3) Interactions with non-polar compounds (EL)

2

EL = -

Qi j

2 (4 0)2 r4

(B) Electron transfer (sharing electron)

(soft interactions)

non-polar

5. Lewis acid-base interactions

EAB = - [EA* EB + CA* CB], Approximation for A-B interaction
Where: EA* EB = Measures of acid (A) and base (B)s ability
to undergo hard acid-base interaction
CA* CB = Measures of acid (A) and base (B)s ability
to undergo soft acid-base interaction
The values of EA, EB, CA, CB:
Rel. Acidity
EA
CA
HF
Alcohols
Phenols
SO2
Iodine

17.0
3.6
4.7
1.1
1.0

0.0
0.8
1.7
7.2
10.0

Rel. Basicity
EB
CB
Ammonia
Ketones
1 Amines
2 Amines
3 Amines
Esters
Sulfides

1.3
0.7
1.2
0,9
0,6
0.6
0.0

0.3
0.1
0.6
0,9
1.2
0.4
0.8

Strong interactions: hard-hard interactions, and soft-soft interactions

Weak interactions: hard-soft interactions.

Distribution equilibria and Solubility

0

-i - i ext
K = exp
RT

distribution coefficient

Solubility: i dissolved in j

G = H TS
H =

TS = RT ln (Ci)
0

G = + RT ln (Ci)
At soluble equilibrium:

G = + RT ln (Ci) = 0
-
Ci = exp
RT

-0
-0
i = Hi TSi
0

A---B

H = EL +EI + ED + EAB

A + B

Distribution equilibrium and Solubility

-0
-0
i = Hi TSi
0

A---B

A + B

H = EL +EI + ED + EAB
Possible interactions

Type of Compounds

EL, EI, ED, EAB

Acid-base compounds
Non Acid-base
Permanent dipole moment
Polar compounds
Non-Polar compounds

Relative strength
Strong

EL, EI, ED

EL

Weak

For all of the above interactions are present in one compounds

EL < EI < ED < EAB

Quantitative Approach for the Strength

of Molecular Interactions
A more quantitative approach in estimating the strength of
molecular interactions is to use various scales that decribe
molecular polarity.
(a) Polarizability
(b) Dipole Moments
(c) Solubility parameters
(a) Polarizability
(1) The polarizability ()of a compound is a measure of how
easily the electron clouds of a compound may be distorted
(2) The value of for any atom or molecules can be calculated
fromspectroscopica properties, such as its refractive index.
(i)v = [3 N/4][(n2-1)/(n2+2)]
Where, (i)v = polarizability of the compound per unit volume
N = Avogadros number
n = refractive index of the compounds

Dispersion interaction (London forces)

EL = - CL Vi (i)v (j)v between two molecules
Where: (i)v (j)v = polarizability of i (solute) and j (solvent) per unit volume
CL: Dispersion constant (uniform for most compounds)
Vi = Molar volume of i (MW/density)
Note: it is useful in predicting boiling points and solubility of non-polar
compounds, such as saturated aliphatics.
MW
Compound (g/mol)
Ethane

Density
(g/mL)

Refractive
Index

Boiling Points
(oC)

30.07

0.572

1.0377

-88.6

Octane 114.23

0.7025

1.3974

125.7