CHAPTER 9

Solutions

SOLUTIONS
Solution = Homogeneous mixture

one phase (s, l, g)

more than 1 component

Molecular interactions play a central role Solution composition

ni mole fraction: xi = ntot

SOLUTIONS
Partial molar quantities separated components mixture

n1 , n2 , . . . , nr Vm,1 , Vm,2 , . . . , Vm,r V = n1 Vm,1 + n2 Vm,2 + + nr Vm,r

SOLUTIONS
Partial molar quantities separated components mixture

n1 , n2 , . . . , nr Vm,1 , Vm,2 , . . . , Vm,r

V =V
because of interaction differences, rearrangements, ...

V =
i=1

ni Vm,r

SOLUTIONS
Partial molar quantities separated components mixture

n1 , n2 , . . . , nr Vm,1 , Vm,2 , . . . , Vm,r

V =V U =U H=H S=S G=G A=A

V =
i=1

ni Vm,r

SOLUTIONS
Partial molar quantities mixture

V = V (T, P, n1 , n2 , . . . , nr ) U = U (T, P, n1 , n2 , . . . , nr )
similarly for H, S, G, A, etc.

dV =

V T

dT +
P,ni

V P

dP +
T,ni

V ni

P,T,nj =i

dni + +

V nr

dnr
P,T,nj =r

SOLUTIONS
Partial molar quantities mixture

X = V, U, H, etc.

i = X

X ni

P,T,nj =i

For a pure substance:

i = Xm,i X
(except ideal gases)

In a mixture:

i = Xm,i X

SOLUTIONS
Partial molar quantities mixture

X = V, U, H, etc.

i = X

X ni

P,T,nj =i

X
r

i ? X

n=
i=1

ni

X = nf (T, P, x1 , x2 , . . . , xr )

SOLUTIONS
Partial molar quantities

V = nf (T, P, x1 , x2 , . . . , xr )
T, P and xi constant: but

dV = f (T, P, x1 , x2 , . . . , xr )dn V P
r i=1

dV =

V T

dT +
P,ni

dP +
T,ni

i dni V

dni = xi dn + ndxi
r

dV =
i=1

i dn xi V

f (T, P, x1 , x2 , . . . , xr )dn =
i=1

i dn xi V

SOLUTIONS
Partial molar quantities

f (T, P, x1 , x2 , . . . , xr )dn =
i=1

i dn xi V

f (T, P, x1 , x2 , . . . , xr ) =
i=1

i xi V

V =
i=1

i = nxi V

r i=1

i ni V

SOLUTIONS
Partial molar quantities separated components mixture

mix V mix V

=V

V i ni (V
i

=
i

i ni V
i

ni Vm,i =

Vm,i )

SOLUTIONS
Partial molar quantities separated components mixture

mix X

=X

X =
i

i ni (X

Xm,i )

Due to molecular interactions and entropy changes

SOLUTIONS
Partial molar quantities

i = G

G ni

= i
T,P,nj =i

fundamental quantity that leads to all other thermodynamic properties of a solution

T and P constant:

G=
i

ni i

G=H

TS

G ni

i = H i = i = G
T,P,nj =i

i TS

SOLUTIONS
Partial molar quantities

i = H i i = G i G = T P,nj=i i G = P T,nj=i

i TS i T

=
P,nj =i

i S

i P

i =V
T,nj =i

SOLUTIONS
Mixing quantities

mix G

mix H

T Smix

mix G

=
P,nj

Smix

the changes are due to differences in the interactions

mix G

=
T,nj

Vmix

SOLUTIONS
How to determine partial molar quantities

Partial molar volume

Slope method From mixV

Partial molar enthalpy, entropy and Gibbs energy

Hmix =
i

i ni (H

A Hm,i ) = nA (H

B Hm,A ) + nB (H

Hm,B )

It is only possible to determine the enthalpy of a solution relative to the enthalpy of the pure components Similar equations for S and G

SOLUTIONS
How to determine partial molar quantities

Integral heat of solution per mole of B

Hint,B =

mix H

nB

Heat adsorbed by the system when 1 mole of pure B is added at constant T and P to pure A to produce a solution of the desired mole fraction xB Integral heat of solution ad infinite dilution

Hint,B = lim xA

Hint,B

SOLUTIONS
How to determine partial molar quantities

Differential heat of solution per mole of B

B Hdif f,B = H

Hm,B

Enthalpy change per mole of added B when B is added at constant T and P to a solution of fixed composition xB Differential heat of solution ad infinite dilution

Hdif f,B = lim xA

Hdif f,B

Hdif f,B =

Hint,B

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 constant T & P

mix V

mix U

mix H

=0

like ideal gases, but broader definition

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 constant T & P

mix V

mix U

= =?

mix H

=0

mix S

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 constant T & P

mix V

mix U

mix H

=0

mix S

=0

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 constant T & P

mix V

mix U

mix H

=0

mix S

=0 ni ln xi
i

from experiments

mix G

= RT = R

mix S

ni ln xi
i

SOLUTIONS
Ideal solutions

Lets find the equivalent thermodynamic definition (constant T & P)

mix G

= RT
i

ni ln xi

mix G

=
i

i ni (G

Gm,i )

RT
i

ni ln xi =
i

ni (i

i )

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

SOLUTIONS
Ideal solutions Thermodynamic properties standard state: pure liquid or solid at temperature T and pressure P of the solution

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

SOLUTIONS
Ideal solutions Thermodynamic properties mixing quantities:

mix V mix G mix S

mix U

mix H

=0

= RT
i

ni ln xi ni ln xi
i

SOLUTIONS
Ideal solutions Thermodynamic properties vapor pressure: decrease P above a solution until it begins to vaporize vapor y1, y2, ..., yN liquid x1, x2, ..., xN

P = P1 + P2 + ... + PN l v i = i i (P, T ) + RT ln xi =
l i

Pi + RT ln P

pure vapor Pi*

i (Pi , T ) = i (Pi , T )
l v

pure liquid

i (Pi , T ) =
l

Pi + RT ln P

SOLUTIONS
Ideal solutions Thermodynamic properties vapor pressure: decrease P above a solution until it begins to vaporize

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

i (T, P )
l

Pi i (T, Pi ) + RT ln xi = RT ln Pi
l

SOLUTIONS
Ideal solutions Thermodynamic properties vapor pressure: decrease P above a solution until it begins to vaporize

i (T, P )
l

Pi i (T, Pi ) + RT ln xi = RT ln Pi
l

for condensed phase systems:

i l (T, P )

i l (T, Pi )

Raoults law

Pi = xi Pi

SOLUTIONS
Ideal solutions

PB* P PA* PB PA 0 xB
liq

vapor P = P A + PB

liquid xA & xB

P* are related to the volatility of a substance if PA* > PB*, then A is more volatile than B

SOLUTIONS
Ideally dilute solutions

Solute molecules (B) dont see each other B

xA

A and B interact (different from ideal solutions!) B A-A A-B B-B

Valid assumption only for nonelectrolytes... why?

SOLUTIONS
Ideally dilute solutions

PA

PA*

?
0 xA
liq

PB 1

For the solvent: A For the solute:

= A (T, P ) + RT ln xA

B = fB (T, P ) + RT ln xB

SOLUTIONS
Ideally dilute solutions Standard state For the solvent: A

= A (T, P ) + RT ln xA = A (T, P ) A (T, PA )

A = A + RT ln xA
For the solute:

B = fB (T, P ) + RT ln xB B = B + RT ln xB
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!

SOLUTIONS
Ideally dilute solutions Vapor pressure vapor yA, y1, ..., yN liquid xA, x1, ..., xN

T and P constant

xA xi i

1 0
,liq

liq i

vap i

+ RT ln xi = i

,vap

Pi + RT ln P

,liq

i RT

,vap

Pi = ln xi P

SOLUTIONS
Ideally dilute solutions Vapor pressure vapor yA, y1, ..., yN liquid xA, x1, ..., xN

,liq

i RT

,vap

Pi = ln xi P

Pi =e xi P
,liq ,vap i i RT

,vap ,liq i i RT

Ki (T, P ) = P e

Henrys constant tabulated at 1 bar depends on the solvent

Pi = xi Ki (T, P )

SOLUTIONS
Ideally dilute solutions Vapor pressure

Solvent Raoults law

PA = xA PA Pi = xi Ki (T, P )

P PB PA 0 xB
liq

Solutes Henrys law

KB
Gas dissolved in liquids are usually a good approximation of ideally dilute solutions

SOLUTIONS
Ideally dilute solutions Partial molar quantities Ideal solutions

i = i + RT ln xi i T =
P,nj =i

= i (T, Pi )

i (T )

i S

i = Sm,i S i = Vm,i V i = Hm,i H

R ln xi

i P

i =V
T,nj =i

= =

mix H

=0 ni ln xi

R
i

SOLUTIONS
Ideally dilute solutions Ideally dilute solutions Ideal solutions

i
still true for the solvent

= i (T, Pi )

i (T )

i = Sm,i S i = Vm,i V i = Hm,i H

R ln xi

= =

mix H

=0 ni ln xi

R
i

SOLUTIONS
Ideally dilute solutions Ideally dilute solutions solvent Ideal solutions solute

i = i (T, Pi ) i = Sm,i S i = Vm,i V i = Hm,i H

i (T )

i =

hypothetical state

R ln xi

Vi = V i = V i

i = H i = H i = S S
mix H

from i ideal solutions H

o different

R ln xi =0 =0 =
different from ideal solutions

= =

=0 ni ln xi

mix V mix H

R
i

mix S

SOLUTIONS
Ideally dilute solutions Reaction equilibrium

Kx =
i

(xi,eq )

G =

RT ln Kx

must be interpreted correctly in terms of the appropriate chemical potentials i