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Lehrstuhl für Siedlungswasserwirtschaft

Ingenieurfakultät Bau Geo Umwelt


Technische Universität München

Polarity & Solubility

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility

- The molecules (solutes) polarity


- The solvent
- Temperature
- Pressure
- pH

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility

The solubility of a solute (= solved compound) highly depends on its properties (e.g. its polarity)
and the properties of the solvent as well as on the temperature, the pressure and the pH
(„Like dissolves like“). A substance can be solved up to a specific and solute- and solvent
dependent maximum concentration (=saturation concentration).

Polarity describes the electric charge distribution within a molecules, which is dependent on
the electronegativity of its containing atoms. Polar molecules can form e.g. hydrogen bonds
(compare slides „Polarity Basics“)

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility

Solvent classification according to polarity


Solvents are generally classified into „polar“ and „non-polar“. Different scales are available
for more detailed classification, e.g. polarity of a solvent is roughly reflected by its dielectric
constant/static permittivity (= the measure of its chemical polarity).

Elutropic series of solvents


The elutropic series of solvents reflects the ability of a solvent to elute various solutes from
a given sorbent („eluting power“/„solvent strength“) (compare slides „Chromatography“).
Although the eluting power depends on the stationary phase as well as on the compounds,
the order is usually from polar solvents (e.g. water or methanol) to non-polar solvents
(e.g. hexane).

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


Polarity of solvents according to dielectric constant/static permittivity
Dielectric constant/static permittivity:
Polar solvents δ− H H
dielectric constant

e.g. O δ+ δ− δ+ δ+ δ−
Water H C O H H C C N
Decreasing

Methanol H Hδ+
δ+
Ethanol Water H H
Acetonitrile Methanol Acetonitrile
dielectric constant

Non-polar solvents CH3


δ−
e.g. Cl H H H H H H
δ+
Decreasing

Chloroform
Toluene δ−
Cl C H H C C C C C C H
Hexane
Cl H H H H H H
δ−
Chloroform Toluene Hexane
logD calculation and drawing of chemical structures was performed with „MarvinSketch 14.8.25.0“, ChemAxon (www.chemaxon.com)
PD Dr. J. Graßmann; PD Dr. T. Letzel
Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


Classification of solute solubility

Partition coefficient
log P refers to neutral, non-ionizable molecule species
Lipophilicity/hydrophilicity of a molecules is determined according to its distribution in a
biphasic system, consisting of two immiscible solvents (e.g. octanol and water)

Partition coefficient (log P) =

𝑠𝑜𝑙𝑢𝑡𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑖𝑛 𝑜𝑐𝑡𝑎𝑛𝑜𝑙


𝑠𝑜𝑙𝑢𝑡𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟
octanol soluteneutral

log P < 0 log P > 0


water soluteneutral Hydrophilic Hydrophobic
-2 -1 0 1 2

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


Classification of solute solubility

Distribution coefficient
log D refers to ionizable molecules (Lipophilicity and therefore solubility changes as a
function of pH for ionisable compounds)
Distribution coefficient (log D) =

𝑠𝑜𝑙𝑢𝑡𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑙𝑙 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑖𝑛 𝑜𝑐𝑡𝑎𝑛𝑜𝑙


𝑠𝑜𝑙𝑢𝑡𝑒 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑙𝑙 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑖𝑛 𝑤𝑎𝑡𝑒𝑟
octanol soluteionized + un-ionized

water soluteionized + un-ionized


log D < 0 log D > 0
Hydrophilic Hydrophobic
-2 -1 0 1 2

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


pH

pH reflects the concentration of hydrogen ions (H+)/hydroxyl ions (OH-) in the solution.
The proton (i.e. H+) concentration increases with decreasing pH.

H+ + OH− ⇋ H2O

Increasing acidity neutral Increasing basicity

pH 0 7 14
Hydrogen ion concentration [H+] 100 10-7 10-14

H+
OH-

Hydroxyl ion concentration [OH-] 10-14 10-7 100

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


pKa

pKa is the pH at which the abundance of ionized and non-ionized from is equal
e.g. acetic acid (CH3COOH) with a pKa of 4.8

H O H O

- -
- -
H-C-C H-C-C -
H OH H O
100
Abundance [%]

50

0
4.8
Protonisation of carboxylgroup Deprotonisation of carboxylgroup
at low pH, i.e. high H+ concentration pH of solution at high pH, i.e. low H+ concentration
 Molecule is neutral  Molecule is negatively charged

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

pH dependence of log D Polarity & Solubility


e.g. Acetic acid
Increasing pH results in ....

.... increasing abundance of


negatively charged acetic acid
molecules (see also slide 8)

.... decreasing logD


(-0.22 at pH 1.5 to
-3.75 at pH 10)

.... increasing solubility of acetic acid


in aqueous solution
(compare slide 6)

logD calculation was performed with „MarvinSketch 14.8.25.0“, ChemAxon (www.chemaxon.com)

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


Examples of logD values of molecules at physiological pH 7.4

Substance Structure logD at pH 7.4

Caffeine Neutral at pH 7.4 -0.55

Majority is positively
Adrenaline charged at pH 7.4 -1.63
+

Vitamine A 4.69
Neutral at pH 7.4

logD calculation and drawing of chemical structures was performed with „MarvinSketch 14.8.25.0“, ChemAxon (www.chemaxon.com)
PD Dr. J. Graßmann; PD Dr. T. Letzel
Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


Isoelectric point (pI)

pI is the pH at which a molecule carries no net electrical charge. At a pH below the pI, the
molecule will carry a positive charge. At a pH above the pI, it will carry a negative charge.
e.g. amino acid alanine (pI = 6.0)

+NH +NH NH2


3 3
-
H3C C COOH H3C C COO- H3C C COO
H H H
cation zwitterion anion
pH < pI pH = pI pH > pI

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


Isoelectric point (pI)
e.g. Alanine

logD << 0 at all pH values

good water solubility

lowest solubility at neutral


net charge (logD of -2.84)

logD decreases at pH above


and below pI (= pH 6.0)
 water solubility increases
for molecules with positive
or negative net charge
logD calculation was performed with „MarvinSketch 14.8.25.0“, ChemAxon (www.chemaxon.com)
PD Dr. J. Graßmann; PD Dr. T. Letzel
Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


„Like dissolves like“
e.g. Vitamins are classified into water soluble (hydrophilic) and fat soluble (hydrophobic)

logD (pH 7.4) Soluble in


e.g. ethanol,
Vitamin A 4.69 methanol,
„fat soluble“
chloroform

e.g. ethanol,
Vitamin D3 7.13 acetone, DMSO,
„fat soluble“ chloroform

logD calculation and drawing of chemical structures was performed with „MarvinSketch 14.8.25.0“, ChemAxon (www.chemaxon.com)
PD Dr. J. Graßmann; PD Dr. T. Letzel
Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


„Like dissolves like“
e.g. Vitamins are classified into water soluble (hydrophilic) and fat soluble (hydrophobic)
logD (pH 7.4) Soluble in

Vitamin C e.g. water,


-4.83 methanol,
„water soluble“
ethanol

e.g. water,
Vitamin B7 -2.57
ethanol
„water soluble“

good solubility
at high pH due to
2 negative charges alkaline
-3.67 solution

logD calculation and drawing of chemical structures was performed with „MarvinSketch 14.8.25.0“, ChemAxon (www.chemaxon.com)
PD Dr. J. Graßmann; PD Dr. T. Letzel
Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


„Like dissolves like“

Solvent properties

Solute Polar Non-polar

properties

Ionic Soluble Insoluble

Polar Soluble Insoluble

Non-polar Insoluble Soluble

PD Dr. J. Graßmann; PD Dr. T. Letzel


Lehrstuhl für Siedlungswasserwirtschaft
Ingenieurfakultät Bau Geo Umwelt
Technische Universität München

Polarity & Solubility


Further factors that affect solubility ....

- Temperature

With increasing temperature of water or solvent the dielectric constant/static


permittvity of water decreases.
 Water becomes less polar
 Increasing solubility of non-polar compounds
(Relevant for applications like e.g. high-temperature chromatographic separation,
in which a temperature gradient is applied to a chromatographic column situated in
a column oven)

- Pressure

The effect of pressure on the solubility is only minor and is therefore negligible

PD Dr. J. Graßmann; PD Dr. T. Letzel