CHAPTER 10

Nonideal solutions

NONIDEAL SOLUTIONS
Ideal solutions Solution where the molecules of the various species are so similar to one another that replacing molecules of one species with molecules of another species will not change the spatial structure of the intermolecular interaction energy in the solution

mix V

mix U

mix H

=0

mix G

= RT
i

ni ln xi ni ln xi
i

mix S

i = i (T, P ) + RT ln xi
i

Raoults law

= i (T, P )

Pi = xi Pi

NONIDEAL SOLUTIONS
Ideally dilute solutions Solute molecules (B) dont see each other B

xA

A and B interact: A - A and A - B only B

For the solvent:

A = A + RT ln xA B = B + RT ln xB

(as for ideal solutions)

For the solute:

(Holds only near xB 0)

defines a hypothetical state at T and P in which B keeps the same properties as in the very dilute solution although xB 1. It depends on the solvent!

NONIDEAL SOLUTIONS
Ideally dilute solutions

mix V
B

=0 =0 =0
Henrys law

mix H mix U

Pi = xi Ki (T, P )

For the solvent:

A = A + RT ln xA B = B + RT ln xB

(as for ideal solutions)

For the solute:

(Holds only near xB 0)

defines a hypothetical state at T and P in which B keeps the same properties as in the very dilute solution although xB 1. It depends on the solvent!

NONIDEAL SOLUTIONS
Nonideal solutions (non electrolytes)

i = i + RT ln xi

i = i + RT ln ai i = ai =
same as for ideal or ideally dilute solutions (depending on the case)

activity

ai = ai (T, P, x1 , x2 , . . . , xn )

ai

xi

in the appropriate limits

NONIDEAL SOLUTIONS
Activity

ai = ai (T, P, x1 , x2 , . . . , xn ) ai xi
in the appropriate limits

ai (1) from measurements (2) from statistical mechanics (complicated!)

The behavior of real solutions is studied relative to that of ideal solutions

Activity coefficient

ai =
i

i xi

in the appropriate limits

NONIDEAL SOLUTIONS
Convention I separated liquids solution

all fractions of the components can vary over a considerable range

i = i + RT ln ai = i + RT ln
standard state i = i (T, P ) for all components activity coefficient

i xi
ideal solutions

I,i

xi

1 1

I,i

=1

at all xi

NONIDEAL SOLUTIONS
Convention II For the solvent B

= A (T, P ) A as xA
II,A

A
B

1 1

1 as xA

For the solutes

i =

fictitious state that corresponds to pure solute i in which each i molecule experiences the same intermolecular forces it experiences in an ideally dilute solution in the solvent A

II,i

1 as xA

NONIDEAL SOLUTIONS
How to determine Convention I

PB* PA* PB PA 0 xB
liq

Analysis of liquid - vapor equilibria Raoults law

Pi = xi Pi

Pi = ai Pi

Pi = constant at constant T

NONIDEAL SOLUTIONS
How to determine Convention I

1/PB* 1/PA* aB aA 0
ai =
i xi

Analysis of liquid - vapor equilibria Raoults law

Pi = xi Pi

Pi = ai Pi

Pi = constant at constant T

xB

liq

1
Pi =
(l ) i xi Pi (v ) P xi

(l ) i xi Pi

NONIDEAL SOLUTIONS
How to determine Convention I

1/PB* 1/PA* aB aA

Analysis of liquid - vapor equilibria

Pi =
(id) but Pi

(l ) i xi Pi

=
i

(l ) xi Pi

Pi
(id) Pi

0
Pi < Pi >

xB
(id) Pi (id) Pi

liq

1
i i

<1 >1

i < i >

(id) i (id) i

NONIDEAL SOLUTIONS
How to determine Convention II Analysis of liquid - vapor equilibria Raoults law

PA

PA*

Solvent:

PA = aA PA =
Ideally dilute

A xA PA

PB 1

Solutes:

Pi = ai Ki =

i xi Ki

xA

liq

NONIDEAL SOLUTIONS
Gibbs - Duhem equation In an equilibrium mixture the partial molar quantities are not independent of one another

G=
i

ni i
T & P fixed

dG =
i

(ni di + i dni )

Chapter 4:

dG =

SdT + V dP +
i

i dni

ni di = 0
i

changes in the chemical potential of the solution components are not independent

NONIDEAL SOLUTIONS
Gibbs - Duhem equation In an equilibrium mixture the partial molar quantities are not independent of one another

G=
i

ni i
T & P fixed

dG =
i

(ni di + i dni )

Chapter 4:

dG =

SdT + V dP +
i

i dni

i = 0 ni d Y
i

changes in partial molar quantities of the solution components are not independent

NONIDEAL SOLUTIONS
Gibbs - Duhem equation Application: Find the activity coefficient for a non-volatile component

xA dA + xB dB = 0

i = i + RT ln xi + RT ln

dxA dA = RT + RT d(ln xA dxB dB = RT + RT d(ln xB

B)

A)

B)

dxA + xA d(ln xA + xB = 1

A)

+ dxB + xB d(ln dxA + dxB = 0

=0

NONIDEAL SOLUTIONS
Gibbs - Duhem equation Application: Find the activity coefficient for a non-volatile component

dxA + xA d(ln

A)

+ dxB + xB d(ln

B)

=0

integrate from state 1 to state 2

ln

II,B,2

ln

II,B,1

=
1

xA d ln 1 xA

II,A

state 1 = pure solvent

II,B,1

=1

other ways to find the activity coefficients are discussed in the book

NONIDEAL SOLUTIONS
Other concentration scales for solutes

i = II,i + RT ln(
Solute molality:

II,i xi )

ni xi mi = = n A MA xA MA

xi = xA MA

i = II,i + RT ln (

II,i mi xA MA m

/m )

1mol/Kg

i = II,i + RT ln (MA m ) + RT ln (xA

II,i mi /m

NONIDEAL SOLUTIONS
Other concentration scales for solutes

i = II,i + RT ln (MA m ) + RT ln (xA

II,i mi /m

m,i
m,i

II,i + RT ln (MA m ) xA
II,i

i = m,i + RT ln (
m,i

m,i mi /m

1 as xA 1mol/Kg

NONIDEAL SOLUTIONS
Other concentration scales for solutes Molality

i = m,i + RT ln (
m,i

m,i mi /m

1 as xA 1mol/Kg

Molar concentration

i = c,i + RT ln (
c,i

c,i ci /c

1 as xA 1mol/dm3

NONIDEAL SOLUTIONS
Solutions of electrolytes

Strong electrolyte: Solute essentially entirely separates into ions that get then solvated

X +

z+ M + +

Xz

NONIDEAL SOLUTIONS
Solutions of electrolytes

Strong electrolyte: Solute essentially entirely separates into ions that get then solvated

X +

z+ M + +

Xz

BaSO4 Ba2+ + SO42-

Because of the strong long-range interactions between ions, activity coefficients must always be used, even for very dilute solutions

NONIDEAL SOLUTIONS
Solutions of electrolytes

Strong electrolyte: Solute essentially entirely separates into ions that get then solvated

X +

z+ M + +

Xz

Weak electrolyte: only some of the solute separates into ions that get then solvated

+A

z+

equilibrium between undissociated and dissociated species

NONIDEAL SOLUTIONS
Solutions of electrolytes How can we calculate the chemical potential of the different species in solution? Strong electrolytes

+M

z+

Species in solution: A, Mz+ and Xz-

A =

G nA

T,P,n+ ,n
Not possible! We cannot change the number of moles of one ion keeping the number of moles of the other ion fixed

+ =? =?

G n+

T,P,nA ,n

NONIDEAL SOLUTIONS
We can define the chemical potential of the electrolyte as a whole (in solution)

X +

z+ M + +

Xz i = G ni

[M

(sln)]

i = electrolyte

T,P,nA

Similarly for other partial molar quantities, for example:

i = V

V ni

T,P,nA

NONIDEAL SOLUTIONS
We can define the chemical potential of the electrolyte as a whole (in solution)

X +

z+ M + +

Xz i = G ni

[M

(sln)]

i = electrolyte

T,P,nA

Gibbs equation

dG =

SdT + V dP +
i

i dni

For a solution containing A, Mz+ and Xz-

dG =

SdT + V dP + A dnA + + dn+ + dn

NONIDEAL SOLUTIONS
For a solution containing A, Mz+ and Xz-

dG =
But

SdT + V dP + A dnA + + dn+ + dn =

z+ M + +

X +

Xz

dn+ = dn =

+ dni

dni

dG =

SdT + V dP + A dnA + (

+ +

)dni

constant T, P and number of solvent molecules

i =

G ni

=
T,P,nA

+ +

NONIDEAL SOLUTIONS
For a solution containing A, Mz+ and Xz-

i =

G ni

=
T,P,nA

+ +

X +

z+ M + +

Xz

(M

+ (M

z+

)+

(M

NONIDEAL SOLUTIONS
Explicit expression for the chemical potential Solution containing A, Mz+ and Xz-

Molar fraction scale for the solvent

A = A (T, P ) + RT ln (
x,A )

x,A xA

=1

(i.e., xA

1) )

Molality scale for the solute species

+ = + + RT ln ( = + RT ln (

molality scale activity coefficient

+ m+ /m

m /m ) = =
+ +

m = 1 mol/kg
standard state

m,+ m,

=1

NONIDEAL SOLUTIONS
Explicit expression for the chemical potential Problem

+ ,
+,

cannot be determined experimentally! cannot be measured!

Additional definition Stoichiometric molality Mean ionic activity coefficient

ni mi = wA

+ +

NONIDEAL SOLUTIONS
Explicit expression for the chemical potential Additional definition Stoichiometric molality Mean ionic activity coefficient

ni mi = wA

+ +

= Ba2+ + 2N O3
3

Ba(N O3 )2
+

=1 =2

=3

= =(

1 2 + 1 2 1/3 ) +

NONIDEAL SOLUTIONS
Explicit expression for the chemical potential

i =

G ni

=
T,P,nA

+ +

Molality scale for the solute species

+ = + + RT ln ( = + RT ln (

+ m+ /m

m /m ) m+ m m m
+ mi

i =

+ +

+ + RT ln

m+ = m =

mi

NONIDEAL SOLUTIONS
Explicit expression for the chemical potential

i =

+ +

+ + RT ln

m+ m

m+ = m =

m m
+ mi

mi

i = i + RT ln

mi m mi m

strong electrolyte

i = i + RT ln

NONIDEAL SOLUTIONS
Explicit expression for the chemical potential strong electrolyte

i = i + RT ln

mi m
parameter of the solution

measurements tables

stoichiometry

i =

fictitious state with

=1 ai =

mi =1 m

activity

mi m

NONIDEAL SOLUTIONS
Gibbs-Duhem equation

nA dA + ni di = 0
Useful to calculate the activity of electrolyte solutes not volatile (very common) For the solvent

A = A + RT ln aA PA = aA PA

Gibbs-Duhem equation solute activity see derivation for nonelectrolyte solutes in the previous lecture

NONIDEAL SOLUTIONS
Debye-Huckel theory

=?

Theoretical calculations are complex Long-range interactions (Coulomb) implies that each molecule (ion) is interacting with everything else All the models are essentially based on Debye-Huckel theory dilute aqueous solutions at 25 oC

log10

molality-scale ionic strength

(Im /m )1/2 0.510z+ |z | Im 1/2 a 1 + 0.328 m A a=

mean ionic diameter

Im

1 = 2

2 zj mj j

NONIDEAL SOLUTIONS
Debye-Huckel theory

=?

dilute aqueous solutions at 25 oC

log10

(Im /m )1/2 0.510z+ |z | Im 1/2 a 1 + 0.328 m A

<< 1

very dilute aqueous solutions at 25 oC

log10

0.510z+ |z |(Im /m )1/2

NONIDEAL SOLUTIONS
Debye-Huckel theory

<1

mi

The chemical potential is less than it would be in a ideally dilute solution

attractive interactions

raises as

mi

increases

hydration (effective higher molality)

NONIDEAL SOLUTIONS
Davies equation (high concentration)

log10

(Im /m )1/2 0.510z+ |z | Im 1 / 2 1+ m

0.3(Im /m )

NONIDEAL SOLUTIONS
Ionic association

+M

z+

(sln) +

(sln)

Ions of opposite charges attract one another Interactions between ions and solvent molecules as well as the increase in entropy favors the dissociation of a strong electrolyte in solution. For weak electrolyte there is an equilibrium

But, also in solution, ions of opposite charges still attract one another...

ion pairs

M z+ (sln) + X z (sln)

M X z+ z (sln)

NONIDEAL SOLUTIONS
Ionic association ion pairs

M z+ (sln) + X z (sln)

Loosely bound pairs of ions

M X z+ z (sln)

The number of ion pairs depends in part on the solvent. For more polar solvents (high dielectric constant) there are fewer ion pairs The presence of ion pairs (which are neutral or more neutral species) reduces the effective number of ions in solution

changes in the thermodynamic relations

NONIDEAL SOLUTIONS
Ionic association

A, M

z+

, X

, MX

z+ z

nA , n+ , n , nIP

Gibbs equation

dG =

SdT + V dP + A dnA + + dn+ + dn + IP dnIP

NONIDEAL SOLUTIONS
Ionic association Gibbs equation

dG =

SdT + V dP + A dnA + + dn+ + dn + IP dnIP

The number of moles of each ion is different from before (without ion pairing)

{
+

n+ = n =

+ ni

nIP nIP
+ )dnIP

ni

dG =

SdT + V dP + A dnA +
equilibrium

+ + dni

dni + (IP

z+

(sln) + X

(sln)

MX

z+ z

(sln)

IP = + +

NONIDEAL SOLUTIONS
Ionic association Gibbs equation

dG =

SdT + V dP + A dnA + (

+ +

)dni

same expression as before (without ion pairing)!!!

i = i + RT ln

still true!!!

m+ m

m m

What does ion pairing do? ion molalities (m+ and m-) are different!!!

NONIDEAL SOLUTIONS
Ionic association

i = =

+ RT ln

m+ m

m m

fraction of positive ions that do not form pairs with negative ions number of moles of positive ions in solution (not paired)

n+ = + ni

nIP = + ni n = ni

n+ = + ni nIP = [ (1

+ ni = (1 )+ ]ni

)+ ni

NONIDEAL SOLUTIONS
i =
i

+ RT ln

m+ m

m m (1

)+ ]ni

number of moles of ions in solution (not paired)

n+ = + ni

n = [

divide by solvent mass

molality of ions in solution (not paired)

m+ = + mi i = i + RT ln

m = [

(1

)+ ]mi

mi m

NONIDEAL SOLUTIONS
Ionic association

i = i + RT ln

mi m
+/

+/

(1

+ )

=1

1 when

actually tabulated, not

=1

(1) deviations of the solution from ideally dilute behavior (2) ion-pair formation

NONIDEAL SOLUTIONS
Standard-state properties of solution components (1) Review of all the pieces we have studied so far (2) Procedures to get fGo, fHo and fSo of solutes in solution starting from the pure separated components of the solute

f GT (i, sln)

m,i (T, P )

Gelem (T ) Helem (T )

H ( i, sln ) H f T m,i (T, P ) Gm,i (T, P ) =

m,i (T, P )

equilibrium between pure solute and a saturated solution

+ RT ln (

m,i,sat mi,sat /m

Gm,i (T, P )
fG

Gelem = ( T, P ) m,i

Gelem + RT ln (

m /m ) m,i,sat i,sat

(i )

fG

(i, sln)

NONIDEAL SOLUTIONS
Standard-state properties of solution components (1) Review of all the pieces we have studied so far (2) Procedures to get fGo, fHo and fSo of solutes in solution starting from the pure separated components of the solute (3) For electrolytes, everything is measured relative to H+(aq)

f GT [H

(aq )] = 0
fG

f HT [H

(aq )] = 0
f G+

f ST [H

(aq )] = 0

For a solute

X H
+

[i(aq )] =

fG

First,

fG

NONIDEAL SOLUTIONS
Nonideal gas mixtures Standard state of each component i at T: pure gas i at T and P = 1 bar with the gas behaving ideally (same standard state as ideal mixtures)

i = i + RT ln ai Pi i = i + RT ln P ai e
activity (i i )/RT fugacity ideal

fi

ai P

fi i = i + RT ln P

NONIDEAL SOLUTIONS
Nonideal gas mixtures

fi i = i + RT ln P
i

= =

fugacity coefficient

fi =

i Pi

i (T, P, y1 , y2 , . . . , yn )

measure of the deviations from the ideal behavior (like i )

fi

Pi as P
ideal behavior

Pi i = i + RT ln + RT ln P i = fi
id i

+ RT ln

Pi e

(i id i )/RT

NONIDEAL SOLUTIONS
Nonideal gas mixtures

fi i = i + RT ln P fi ,
from experiments

i P

i =V
T,nj

i dP di = V fi =
i Pi

di = RT d ln fi i V d ln fi = dP RT

i yi P

i V d ln i + d ln yi + d ln P = dP RT

NONIDEAL SOLUTIONS
i V d ln i + d ln yi + d ln P = dP RT
constant composition Nonideal gas mixtures

d ln

i dP V = + dP P RT
2

integration from state 1 to state 2 state 1

d ln

i V RT
P2

1 P

1 P

dP

i V
from experiment

P1 = 0 i,1 = 1

ln

i,2

i V RT

dP

NONIDEAL SOLUTIONS
Nonideal gas mixtures

For the special case of a one-component nonideal gas mixture

i = Vm V ln

P2

Vm RT

1 P

dP

In all liquid-vapor equilibrium equations, to take non-ideality of the vapor phase into account

Pi

fi Pi = fi =
(liq ) Pi I,i xi (liq ) Pi I,i xi

When the vapor was considered to be ideal:

Now, the non-ideality of vapor is also considered: