Chapter 5: Aqueous Solubility

equilibrium partitioning of a compound between its pure phase and water

KH = PoL/Csatw Kow = Csato/Csatw Koa = Csato/PoL

Air
A gas is a gas is a gas T, P KH PoL Koa

Octanol
NOM, biological lipids, other solvents T, chemical composition

Water
Fresh, salt, ground, pore T, salinity, cosolvents Kow

Csatw

Pure Phase (l) or (s)

Ideal behavior

Csato

water
covers 70% of the earths surface is in constant motion is an important vehicle for transporting chemicals through the environment

Solubility
is important in its own right will lead us to Kow and Kaw

Relationship between solubility and activity coefficient

Consider an organic liquid dissolving in water:

Q iL ! Q *iL  RT ln K iL xiL
* iw i

for the organic liquid phase for the organic chemical in the aqueous phase

ln K iw xiw
0 ln K iw xiw 

at equilibrium (maximum solubility):

iw

ln K i xi
At saturation!

xisat RT ln K iL RT ln K isat ! ln xiL RT

sat xiw ln xi

sat RT ln K i  RT ln K iw RT

Assume: xiL = 1 and KiL = 1

ln x

sat iw

RT ln K  RT

sat iw

G  RT

E , sat iw

Solubility = excess free energy of solubilization (comprised of enthalpy and entropy terms) over RT The relationship between solubility and activity coefficient is:

sat iw

1 K
sat iw

or

sat i

1 ! sat V Ki

for liquids

The activity coefficient is the inverse of the mole fraction solubility

Solids
must account for the effect of melting of solid i.e. additional energy is needed to melt the solid before it can be solubilized:
C ( L) ! C ( s) e
sat i sat i  ( fus Gi / RT

At any given temperature

* piL ( fus Gi ! RT ln pis

p C ( L) ! C ( s ) pis
sat i sat i

* iL

Recall Prausnitz:
(S fus (Tm ) Tm p s0 ln 0 !   1 p R T

Phase change costs

or

Why bother with the hypothetical liquid?

Melting point vs. boiling point

Naphthalene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz[a]anthracene Benzo[a]pyrene MW 128.2 166.2 178.2 178.2 202.3 202.3 228.3 252.3 Tm 80.6 113 99.5 217.5 110.8 156 159.8 176.5 Tb 217.9 295 340.2 342

Tm and Tb vs. MW
700 600 500 Tm or Tb (C) 400 300 200 100 0 100 y = 2.768x - 152.94 R2 = 0.9524

435 584

y = 0.6573x + 13.002 R2 = 0.3016 120 140 160 180 MW (g/m ol) 200 220 240 260

Gases
solubility commonly reported at 1 bar or 1 atm (1 atm = 1.013 bar)
O2 is an exception

the phase change advantage of condensing the gas to a liquid are already incorporated. the solubility of the hypothetical superheated liquid (which you might get from an estimation technique) may be calculated as:

p C ( L ) ! Ci pi
sat i pi

* iL

theoretical partial pressure of the gas at that T (i.e. > 1 atm) Actual partial pressure of the gas in your system

concentration dependance of K
In reality, Kat saturation { K at infinite dilution

However, for compounds with K > 100 assume: K at saturation = K at infinite dilution i.e. solute molecules do not interact, even at saturation

Molecular picture of the dissolution process

The two most important driving forces in determining the extent of dissolution of a substance in any liquid solvent are an increase in disorder (entropy) of the system compatability of intermolecular forces of attraction.

Ideal liquids
The solubility of ideal liquids is determined by energy lowering from mixing the two substances. For ideal liquids in dilute solution in water, the intermolecular attractive forces are identical, and (Hmix = 0. The molar free energy of solution is:

(Gs = (Gmix= -T(Smix = RT ln (Xf/Xi)

(Gs ,(Gmix = Gibbs molar free energy of solution, mixing (kJ/mol) -T(Smix = Temperature v Entropy of mixing (kJ/mol) R = gas law constant (8.414 J/mol-K) T = temperature (K) Xf, Xi = solute mole fraction concentration final, initial

Note: mole fraction of solvent } 1 for dilute solutions (dilute solution has solute conc <10-3 M)

dissolution
solute solvent

two-phase form - low disorder

solution form high disorder

The greater the dilution, the smaller (i.e., more negative) the value of (Gs and the more spontaneous in the dissolution process

Nonideal liquids
The intermolecular attractive forces are not normally equal in magnitude between organics and water. (Gs { (Gmix (no longer equal) Instead: (Gs = (Gmix + (Ge (Ge = Excess Gibbs free energy (kJ/mol) (Gs = (Hs - T(Ss = (He - T((Smix + (Se) (He, (Se = Excess enthalpy and excess entropy (kJ/mol) (He = intermolecular attractive forces; cavity formation (solvation) (Se = cavity formation (size); solvent restructuring; mixing

Entropy: Enthalpy: For small molecules, enthalpy term is small ( 10 kJ/mol) Entropy term is generally unfavorable Seems odd? Water forms a flickering crystal around the compound, which fixes both the orientation of the water and of the organic molecule

Only for large molecules is enthalpy significant (positive)

Solubility Process
A mechanistic perspective of solubilization process for organic solute in water involves the following steps: a. break up of solute-solute intermolecular bonds b. break up of solvent-solvent intermolecular bonds c. formation of cavity in solvent phase large enough to accommodate solute molecule d. vaporization of solute into cavity of solvent phase e. formation of solute-solvent intermolecular bonds f. reformation of solvent-solvent bonds with solvent restructuring

Estimation technique
Activity coefficients and water solubilities can be estimated a priori using molecular size, through molar volume (V, cm3/mol). Molar volumes in cm3/mol can be approximated: Vi ! ( N ij )(aij )  (nij )(6.56)
Ni = number of atoms of type i in jth molecule ai = atomic volume of ith atom in jth molecule (cm3/mol) nj = number of bonds in jth molecule (all types)

a values: see p. 149

Solubility can approximated using a LFER of the type:

ln K i ( L) ! a ( size)  b

ln C ( L ) ! c ( size)  d
sat i

Molar volume here must be estimated by the atom fragment technique (see p. 149)

This type of LFER is only applicable within a group of similar compounds:

Another estimation technique

VP describes self:self interactions molar volume describes vdW forces refractive index describes polarity

2 nDi 1 2/3 * ln K i ! ln piL 0.572 ix 2 V n  2 5.78(T i ) Di additional 8.77(E i ) 11.1( F i )  0.0472Vix  9.49

H-bonding

cavity term

polarizability term

Note that this is similar to the equation we used to estimate vapor pressure, but is much more complicated! Also, introduced T, the polarizability term. This approach is universal valid for all compounds/classes/types This approach can also be used (with different coefficients) to predict other physical properties (for example, solubility in solvents other than water).

Factors Influencing Solubility in Water

Temperature Salinity pH Dissolved organic matter (DOM) Co-solvents

Temperature effects on solubility

Generally: as T o, solubility o for solids. as T o, solubility can o or q for liquids and gases.
BUT For some organic compounds, the sign of (Hs changes; therefore, opposite temperature effects exist for the same compound!

The influence of temperature on water solubility can be quantitatively described by the van't Hoff equation as: ln Csat = -(H/(RT) + Const.
C sat T 2 (H 1 1  ln ! C sat T 1 R T1 T2
recall from thermodynamic lecture

What (H is this?
H
E i

the energy (enthalpy) needed to get the liquid (real or hypothetical) compound into aqueous solution
Liquids: Solids: OR

( L H ! H iE

( s H ! H iE  ( fus H i
E ( wa H ! H iw  ( vap H i

gas water
Pure liquid Pure solid

gas

( wa H i
(w Hi

aqueous

( vap H i
( ws H i

( sub H i

liquid solid

( fus H i

Note: sometimes energy states are higher/lower, so some of these enthalpy terms could be negative!

Solids, liquids, gases

Solids
ln C ( s ) ! 
sat iw E ( fus H i  H iw

RT

 cst

Gases

sat ln Ciw ( g ) ! 

gas
l C

Tb

Liquids

E  ( vap H i  H iw

liquid

1/

Tm

ln Cisat ( L) !

H iE  cst RT

RT

 cst

Parameters for this plot:

( fus H i ! 20 kJ/mol
E H iw ! 10 kJ/mol

solid

( vap H i ! 20 kJ/mol

Salinity effects on solubility

As salinity increases, the solubility of neutral organic compounds decreases (activity coefficient increases)

K iw , salt ! K iw 10

 K is [ salt ]tot

typical seawater [salt] = 0.5M

Ks = Setschenow salt constant (depends on the compound and the salt) [salt] = molar concentration of total salt.
s i , sea ater

$
k

s i , salt k

xk

The addition of salt makes it more difficult for the organic compound to find a cavity to fit into, because water molecules are busy solvating the ions.

pH can increase apparent solubity

pH effect depends on the structure of the solute. If the solute is subject to acid/base reactions then pH is vital in determining water solubility. The ionized form has much higher solubility than the neutral form. The apparent solubility is higher because it comprises both the ionized and neutral forms. The intrinsic solubility of the neutral form is not affected. We will talk about this more when we look at acid/base reactions

Dissolved organic matter (DOM) can increase apparent solubility

DOM increases the apparent water solubility for sparingly soluble (hydrophobic) compounds. DOM serves as a site where organic compounds can partition, thereby enhancing water solubility. Solubility in water in the presence of DOM is given by the relation: Csat,DOM = Csat (1 + [DOM]KDOM) [DOM] = concentration of DOM in water, kg/L KDOM = DOM/water partition coefficient Again, the intrinsic solubility of the compound is not affected.

Co-solvent effect on solubility

the presence of a co-solvent can increase the solubility of hydrophobic organic chemicals co-solvents can completely change the solvation properties of water examples:
industrial wastewaters gasohol engineered systems for soil or groundwater remediation HPLC

focus on
sparingly soluble solutes completely water-miscible organic solvents
methanol, ethanol, propanol, acetone, dioxane, acetonitrile, dimethylsulfoxide, dimethylformamide, glycerol, and more
What do these solvents have in common?

In general
solubility increases exponentially as cosolvent fraction increases. need 5-10 volume % of cosolvent to see an effect. extent of solubility enhancement depends on type of cosolvent and solute
effect is greatest for large, nonpolar solutes more organic cosolvents have greater effect propanol>ethanol>methanol

Bigger, more non-polar compounds are more affected by co-solvents

Different co-solvents behave differently, behavior is not always linear

We can develop linear relationships to describe the affect of co-solvents on solubility. These relationships depend on the type and size of the solute

Quantifying cosolvent effect can be complex, so assume log-linear relationship between solubility and volume fraction of cosolvent (fv)
sat sat log xil ( f v ) ! log xil ( f v1 )  W ic ( f v  f v1 )

if fv1 = 0, then we are describing the solubility enhancement relative to the standard aqueous solubility:
sat sat log xil ( f v ) ! log xil  W ic f v

Wic is the slope term, which depends on the both the cosolvent and solute

Problem 5.4
estimate the solubilities of 1-heptene and isooctane (2,2,4 trimethylpentane)
compound MW g/mol 70.1 84.2 84.2 84.2 86.2 100.2 100.2 100.2 112.2 114.2 126.3 128.3 128.3 b C 30 60.7 63.4 53.9 49.7 79.2 80.9 92 121.3 117.6 146.9 143 124 Cs t @ C mg/L 148 78 50 48 12.8 4.4 4.4 3.3 2.7 0.85 1.12 1.42 1.15

isoctane: V = 0.692 g/mL 1-heptene V = 0.697 g/mL Characteristic volumes: H = 8.71 C = 16.35 -per bond = 6.56

1-pentene 2-me-1-pentene 1-hexene 4-me-1-pentene 2,2-dimethylbut ne 2,2-dimepent ne 2,2,3-trime but ne 3-me hexane 1-octene 2-me heptane 1-nonene 3-me octane 2,2,5-trimethylhexane