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Chem131 Chapter9
Chem131 Chapter9
Solutions
SOLUTIONS
Solution = Homogeneous mixture
SOLUTIONS
Partial molar quantities separated components mixture
SOLUTIONS
Partial molar quantities separated components mixture
V =V
because of interaction differences, rearrangements, ...
V =
i=1
ni Vm,r
SOLUTIONS
Partial molar quantities separated components mixture
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
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 )
SOLUTIONS
Partial molar quantities
i = G
G ni
= i
T,P,nj =i
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
mix G
=
T,nj
Vmix
SOLUTIONS
How to determine partial molar quantities
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
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
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
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
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
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 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
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
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
xA
SOLUTIONS
Ideally dilute solutions
PA
PA*
?
0 xA
liq
PB 1
= A (T, P ) + RT ln xA
B = fB (T, P ) + RT ln xB
SOLUTIONS
Ideally dilute solutions Standard state For the solvent: A
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
Pi = xi Ki (T, P )
SOLUTIONS
Ideally dilute solutions Vapor pressure
PA = xA PA Pi = xi Ki (T, P )
P PB PA 0 xB
liq
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
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 )
R ln xi
= =
mix H
=0 ni ln xi
R
i
SOLUTIONS
Ideally dilute solutions Ideally dilute solutions solvent Ideal solutions solute
i (T )
i =
hypothetical state
R ln xi
Vi = V i = V i
i = H i = H i = S S
mix 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