Solution - A solution is a homogeneous mixture of two or more substances.

A solution can exist in any phase.

The major component in a solution is termed solvent (A) and all other
constituents are solute(s) (B, C…).
For solutes to be soluble in a solvent their intermolecular forces (IMF)
Solutions holding the solvent molecules (A-A) to form the condensed state must be broken
to accommodate the solute particles. Also the forces holding the solute together
Chapter 9 (B-B) must be broken as well. These steps demand energy. The solute and
solvent molecules then should then interact to make the ‘accommodation’
possible. That requires a release of energy that would compensate or exceed the
Ideal and Non-ideal total energy demand.
Vapor: gas phase molecule evaporated from solvent.
Gas: gas phase molecule of a different type than from the solvent.

Ideal Solutions – all components volatile case

The driving forces for dissolution are;
a. Entropy gain due to dissolution.
b. Heat release (net attractive or near zero repulsion) due to various
inter-particle interactions such as H-bonding, dipole-dipole,
ion-induced dipole.
London (also known as van der Walls) forces…ever presen).
Similar intermolecular forces in the solvent and solute (A-B  A-A  B-B)
produces ideal solutions.
Deviations from the intermolecular forces mentioned above produces
non- ideal solutions.
P  PA*
The liquid A is in equilibrium with its (saturated)
vapor phase with partial pressure of A (saturated
vapor pressure of pure A at the temperature = P*A).
If another liquid B (that is soluble in A) is added,
P   xi Pi * the partial pressure of A is reduced. The vapor
i phase now contains both A and B; vapor pressure
of A (PA = xAP*A) and vapor pressure of B
(PB = xBP*B) at the temperature of the liquid.
Pi  xi Pi * :Raoult's Law (followed by ideal solutions)
Very dilute solutions are ideal solutions.
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 Chemical Potential i of a Component i in the Gas and Solution Phases: P 
For i = solvent A;  Asolution   *A  RT ln  A*    *A  RT ln x A
Because each i in two phases are in equilibrium, for each component i, P 

For each i, ivap  isoln Relationship between the chemical potential of any component i, in an ideal
solution to the chemical potential of the pure liquid form of component and
For each i in solution,  vap   0  RT ln  Pi  ;  0  chemical potential (g) pure i the mole fraction of that component in the solution.
i i  P0  i
 
 P 
i solution
 i  RT ln  i0 
0
Eq. 1 P 
P  isolution  i*  RT ln  i *   i*  RT ln xi
 Pi *  P 
For pure solvent, vapor. i  i  i
* vap *liq *
 i  i  RT ln  0  Eq. 2
* 0

For i = (solvent/solute);
(Eq. 1 - Eq. 2)  i
solution
P 
Valid equation where all components are volatile and miscible in all proportions.
 P 
 i*  RT ln  i *   i*  RT ln xi  Pi  xi Pi *

 Pi 
ideal solution

Thermodynamics of mixing (ideal solutions; Vmix  0,  H mix  0 )

Summary:
Similar to gaseous mixtures; Gmix  nRT  xi ln xi
i Gmixing  0
 Gmix  miscible
and S mix       nR  xi ln xi S mixing  0
 T  P ,n1 ,n2 ,.. i
Vmixing  0
 Gmix   dGmix   S mix dT  Vmix dP  H mixing  0
Also Vmix    0 :by definition  
 P T ,n1 ,n2 ,..  d Gmix   S mix dT  Vmix dP 
Vmideal  x AVm*, A  (1  x A )Vm*, B
Therefore H mix  Gmix  T S mix
 V   V 
H mix  nRT  xi ln xi  T (  nR  xi ln xi )  0 V  n1    n2   Constants for ideal solutions,
i i  n1   n2  not constant for non ideal solutions
Ideal Binary Solutions P*1
For a binary solution with components 1 and 2 the total vapor pressure is, Ptotal P*2

P1
Where xi = mole fraction in solution, P*i vapor pressure of pure liquid i; x1 and x2.

Pressure
P2  x2 P2*
Mole fraction of each component in the gas phase be y1 and y2;

P2

P1  x1 P1*

Ptotal  P2*  ( P1*  P2* ) x1

100% 1 (x2) 100% 2

P1* Composition of liquid and gaseous phases, xi and yi;

P2* nBliq  nBtot
are not the same in the 2-phase region at a given P.
A  nA
nliq tot

Ptotal  P2*
x1 
P1*  P2*
nBvap  nBtot
1 = benzene
nAvap  ntot
A
P1*
x B ZB yB
+  vap nBliq
n n n n
vap
n B ,n A n tot vap
B
liq
B
vap
A
liq
A xBliq 
P2* ntot
x1 nBvap  nBliq nBvap
y1 ZB  yBvap 
nBliq , nliq nBvap  nBliq  nAvap  nliq
A A ntot
x1
y1
For a binary mixture of i and j Phase rule – for an ideal solution
Average composition Zi of two components (C=2) and
three independent state variables
Zi 
n liq
i  nivap  
ni xbenzene (P, T and Zbenzene).
niliq  nivap  nliq
j  nj
vap
ntotal
F = C - p +2 F=4-p

ybenzene F=3; p=1

F=2; [T]
liq. and vap. co-existence One can change P and Z
region i = benzene (two degrees of freedom) F=2; p=2
j = toluene independently in the regions. F=1; [T]
Still one phase.
One can either change P or Z
Average composition refers to the average from all relevant phases, (one degree of freedom)
liquid and/or vapor phases. independently on the curves.
Two phases

Phase rule – for an ideal solution

of two components (C=2) and *
Pbenzene
three independent state variables more
volatile
(P, T and Zbenzene).

F = C - p +2 F=4-p *
Ptoluene
less
volatile
abcd

x 1 Z1 y1
At b, c; two phase system, composition in phases would change; tie line.
At the extremities of the tie line; xbenzene < ybenzene, vapor enriched with benzene.
Always more of volatile component in vapor phase.
Relative Amounts of Materials in the two Phases Fractional Distillation: Temperature-Composition Diagram

bv A separation technique based on the fact that vapor phase above a solution is
For benzene
richer in the more volatile component.
nBtot  nBvap  nBliq lb
The temperature-composition diagram: temperature of the solution (and vapor)
vs. the average system composition, for a given total vapor pressure.
residue
multiplication, followed by subtraction:
Ptotal=1atm

Tb (K)
tot
nliq lb  nvap
tot
bv ybenzene

xbenzene
Lever Rule!! distillate

less
volatile
residue
Ptotal=1atm
Tb (K)

residue
Zi  ybenzene

Z i  xbenzene
distillate

more
distillate
volatile

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Non-Ideal Solutions: Real Solutions (Binary) The Gibbs-Duhem Equation
Non-similar intermolecular forces of solvent and solute (a) A-B > A-A  B-B In a binary solution the chemical potentials of the two components are related.
or (b) A-B < A-A  B-B would produce non-ideal solutions. Tb vs x plots This is an important result, because it allows the chemical potential of a
shows solutions with azeotropic mixtures, (a) with maximum and nonvolatile solute (with near zero vapor pressure) be determined. For a binary
(b)minimum boiling points. solution, starting with;
Azeotropic mixture is a
residue residue liquid mixture with a
constant (minimum or
maximum boiling point). At constant T, P
Such a mixture will
distillate distill without For a solution made by mixing components 1 and 2, stating from nothing and
distillate
decomposition and fixed ending with n1 and n2 moles, Gibbs energy changes from 0 to G (say),
mole ratio.

Colligative Properties
Colligative properties considered are;
Freezing point depression of the solution
Boiling point elevation of the solution
Osmotic pressure of the solution
Which would yield, Colligative properties of solutions depend on the amount of the non-volatile
solute molecules or ions dissolved in a solvent, and does not depend on their
Because, we get, molecular structure/nature.
Dissolution of a solute in a solvent makes the solution more stable w.r.t. the
i.e. Gibbs –Duhem Equation. pure solvent due to the loss of Gibbs free energy resulting from the increase in
entropy. The solid phase formed at the freezing point and the vapor phase
.. the chemical potentials of the two remain unchanged as no solute is present in the solid and no non-volatile
components are dependent. solute is present in the vapor phase.
Pure Substance
  
 T   0
d    S m dT  Vm dP
 P s
   l
s  T    S m
l  P
 g
g Slopes:
S m , gas > S m ,liquid > S m , solid  
 
With T increase, s  l g

‘solid’ line intersects the ‘solvent’ and ‘solution’ lines at f.p.

At a given temperature the phase
‘gas’ line intersects the ‘solvent’ and ‘solution’ lines at b.p.
with the lowest  is the most stable

Only the liquid chemical potential is affected due to the formation of the solution. Expansions - Chemical Potential Plots at constant P

-225
200 250 300 350 400 450
Chemical Potential mu kJ/mol

-230
Tm
g
-235
gas Tb
solid
-240 solution s
-245
solvent
=pure liquid
-250
T (K)

Free energy – Chemical Potential Plots at constant P (= 1 atm) (xsolvent = 0.9) Tm  Tb
‘solid’ line intersects the ‘solvent’ and ‘solution’ lines at f.p.
‘gas’ line intersects the ‘solvent’ and ‘solution’ lines at b.p.
 non-volatile solute
cool Freezing point depression of the solution

pure solution non-volatile solute

solvent xsolvent< 1 Tm
xsolvent= 1
s
cool pure solution
solvent xsolvent< 1
xsolvent= 1
Tm= Tf = f(xsolvent) ?
At f.p. the solution is in equilibrium with the pure solidified solvent, At f.p. the solution is in equilibrium with the pure solid (solvent), therefore;
therefore;

Rearranging; Tm = f(xsolvent) ?

  G fus    G fus 
Because, s  l (melting/fusion)    
 
  ln xsolvent  1  T     T
1    T 
G   solvent
*
  solid
*
     R   xsolvent 
 xsolvent  P R xsolvent
  
T
  P
 T 
  ? T = Tm  P  P
 xsolvent  P
  ln xsolvent   xsolvent  1
 T   T    ln xsolvent 
Now     
 x x 
 P  solvent solvent  P
x x
      solvent solvent

 xsolvent  P   ln xsolvent  P  xsolvent  P

   G fus  xsolvent ' T
H fus dT '
   dxsolvent
  ln xsolvent  1
  
1 T    T   '

R T '2
      xsolvent 
xsolvent in solution 1
xsolvent Tf
 x P x R T  P
 
solvent solvent
Tf = f.p pure solvent H fus  1 1   1 1  R ln xsolvent
 P ln xsolvent  ln 1       
R  T T f   T T f  H fus
  1 
H fus d   
1 1  T    T  because d  G   H d  1  T f  T R ln xsolvent T R ln xsolvent
     T  T    2 
xsolvent R T   xsolvent  P     TT f H fus Tf H fus
 
 P RT f2 ln xsolvent
1 H fus  T  dxsolvent H fus dT T 
1
     H fus
xsolvent R T 2  xsolvent  P xsolvent R T2

If the molality of the solute is msolute; 1 kg of solvent contains m moles of solute.

    RT f2 ln xsolvent
ln xsolvent  ln 
nsolvent
  ln 
1

T f 
H fus
 nsolvent  nsolute   1  nsolute / nsolvent 
1000 masssolute ln xsolvent   ln 1  msolute M solvent    M solvent msolute dilute solutions
nsolvent  ; nsolute  M = molar mass
M solvent M solute
m = molality
nsolute masssolute M solvent
  msolute M solvent RT f2 M solvent msolute
nsolvent M solute 1000 T f     K f msolute
H fus
 1 
ln xsolvent  ln     ln 1  msolute M solvent  T f   K f msolute
 1  msolute M solvent 
2 3
 ln(1  x )  x   .... = x  x <1
x x
2 3
Kf = freezing point depression constant.
 nsolvent Boiling point elevation of the solution
xi  molalityi
1
xsolvent  
nsolvent  nsolute nsolute The boiling point elevation can be calculated using the logic with the appropriate
1 enthalpy and free energy term and the temperature at which l  g phase
nsolvent
equilibrium occur at 1 atm pressure (standard pressure).
M = molar mass nsolute masssolute M solvent M
m = molality
  molessolute solvent
nsolvent M solute 1000 1000
nsolute
 msolute M solvent
nsolvent
nsolvent 1

nsolvent  nsolute 1  M solvent msolute

Osmotic pressure of the solution

Semipermeable membrane allows movement of small solvent molecules

but do not permit larger solutes to pass through it. When a pod made from a
Vapor pressure (solvent)

semipermeable membrane containing a solute that do not pass through the

membrane is immersed in the pure solvent, the solvent diffuses into the pod
at the start. Eventually this diffusion ends when equilibrium is established.

At equilibrium the pressure is higher in the pod than in the surrounding solvent.
The process of diffusion through the membrane would dilute the solution is
osmosis. The excess pressure in the solution with respect to the solvent
is termed osmotic pressure.
At equilibrium,   solution   solvent
 ssolution
olvent (T , P   , xsolvent )   solvent (T , P )
*
 solvent
solution

Naturally, solution is less compared to solvent (solution side more stable).

 solvent
solution
(T , P   , xsolvent )   solvent
*
(T , P   ) Thus given the opportunity to come to equilibrium by separating them via a
semipermeable membrane there will be a movement of molecules from
 RT ln xsolvent the solvent side to solution side.

 solvent
*
(T , P )   solvent
*
(T , P   )  RT ln xsolvent  solvent Movement to stability (to reach equilibrium) is to equalize the potentials.

This is achieved by developing a higher pressure on the solution side brought

 solvent
solution
(T , P   , xsolvent )   solvent
*
(T , P   )
about by the movement of solvent molecules thro’ the semipermeable
 RT ln xsolvent membrane.
  solvent
*
  solvent
solution

Because dG = -SdT + VdP and d = dGm = -SmdT + VmdP;  RT ln xsolvent  Vm

d    S m dT  Vm dP
solvent , P  , x solution P 
ln xsolvent  ln 1  xsolute    xsolute for dilute solutions
 d    S m dT   V dP
'
nsolute n
   solute
m
for dilute solutions
nsolute  nsolvent
solvent , P solvent P
nsolvent
solvent , P  , x P 

 d   Vm  dP' @ constant T
solvent , P P nsolute
Therefore RT  Vm  RTnsolute  nsolventVm  V 
 solvent
*
(T , P   , x )   solvent
*
(T , P )  Vm nsolvent
  solvent
*
(T , P )   solve
*
nt (T , P   )  RT ln xsolvent

 *
(T , P   , x )  (  solvent
*
(T , P   )  RT ln xsolvent )  Vm nsolute RT
solvent  vant Hoff Equation  V  nsolute RT 
 RT ln x  Vm V
 Non-Ideal Solutions: Real Solutions (Binary – volatile components)
The partial and total pressures above a real (non-ideal) solution differ
Non-similar intermolecular forces of solvent and solute (a) A-B < A-A  B-B considerably from that predicted by Raoult's law. From the thermodynamic
(positive deviation) or (b) A-B > A-A  B-B (negative deviation) would point of view the characteristics of real solutions are as follows;
produce non-ideal solutions, however they may be miscible.
Gmixing  0
Non ideal solutions do not follow the Raoult’s Law. Pi  xi Pi * miscible
S mixing  0
ideal +ve deviation -ve deviation
Vmixing  0
(positive or negative for non-ideal solutions)
Raoult’s Law H mixing  0
x
Vmreal  x AVm*, A  (1  x A )Vm*, B
Vmideal  x AVm*, A  (1  x A )Vm*, B concept of partial molar quantities.
(partial molar volume)

Vm ,mixing  Vmreal  Vmideal  0

x1=1 x1=0 x1=0 x1=1 x1=0 x1=1

Partial molar volumes: Molar volumes in real solutions are dependent on the composition,
Vmix  Vmix  V1  V2   0 real solution  V 
add V1 ( P, T , n1 , n2 )     partial molar volume of componenet 1.
V1, n1,  n1  P ,T ,n2 partial molar volume
 V   V  For a binary solution of general composition n1 and n2 ,
Vmix Vmix  n1    n2   real solution
 n1   n2  Vmix  V  n1V1 ( P , T , n1 , n2 )  n2 V2 ( P , T , n1 , n2 )
V2, n2
 V   V 
 ,   ~ molar volumes of 1 and 2  
Vmix  n1V1 ( P , T , n1 , n2 )  n2 V2 ( P , T , n1 , n2 )  Videal  0
 n1   n2 
Vmix   n V ( P, T , n , n )  n V ( P, T , n , n )    (n V
1 1 1 2 2 2 1 2 1 m ,1 ( P , T )  n2Vm ,2 ( P , T )   0
at constant T,P.
Partial molar volumes (Vi) depend on the concentration of all components
These gradients are not constants for 'real solutions'.
therefore the total volume of the mixture (V) is composition dependent (non
linear).
 Example: Chloroform/acetone mixtures
Example:
Positive deviation acetone

chloroform

Solvent Solvent
Changes in the partial molar volumes with
acetone CS2 concentration – small and not negligible.
As V1 increases V2 decreases and vice versa. Partial molar volumes are related in
Dashed line – Raoult’s Law (ideal solution) the same way as the chemical potentials are related in the Gibbs-Duhem equation.

Gibbs-Duhem Equation

In terms of the partial molar volumes, the Gibbs-Duhem equation

takes the form; PCS 2  xCS 2 k HCS 2 Pacetone  xacetone k Hacetone

x2 Solvent
x1dV1  x2 dV2  0  dV1   dV2 Solvent CS2
x1 acetone

Dashed lines – Raoult’s Law (ideal solution).

Boxes – solvent follows Raoult’s Law – dilute ‘solution’. ideal dilute
Red (straight) line – solute follows Henry’s Law Pi  xi k Hi . solution
Ideal Dilute Solution:
asolvent i
activity coeficient,  solvent  ; asolvent i   solvent xsolvent
Real solution  Ideal solution (can be described precisely). xsolvent
Pi  solvent  1 as xsolvent  1 (or xsolute  0)
isolution  i*  RT ln ; *  refers to the pure component i.
Pi *
Pi  xi Pi * As Psolute  0, xsolute  0 ; real  ideal

For real solutions (non-ideal) Pi  xiP*i. As Psolvent  Psolvent

*
, xsolvent  1 ; real  ideal
Pi
Pi  xi Pi * ; xi  , i = solvent  has no molecular model, should be considered as a correction (fudge) factor
Pi *
to account for the deviation from ideality.
P
define activity, asolvent  i* (for ideal solution asolvent  xsolvent )
Pi isolution  i*  RT ln ai for real solutions, all components.
a
and activity coeficient,  solvent  solvent i
xsolvent