Multicomponent System

A general term Describes a system composing more than 2 components (as compared to a 1 and 2-component system) In electronics, biology and synthetic biology, structural fracture dynamics, chemistry and molecular dynamics, color image system, hydrogeology, material science, etc.etc.

Recall: Delta G and

G G G = = spontaneous = + non spontaneous = 0 in equilibrium G/n

Recall: Gibbs Free Energy

Important in everyday processes where T and P are intrinsic variables A must have fundamental quantity

Recall: dG = -SdT + VdP

Given an expression G (T,P) We can calculate S
(G/T)P

And also V
(G/P)T

Recall: G = H TS
Reverse that:

H = G + TS

We have S, G, and we know that:

U = H PV

So we can calculate all other quantities if we know the Gibbs Free Energy

Recall: Solid-Liquid Equil.

If we take the temperature to be constant and we want to know how G is changing with
dG = -SdT + VdP dG = VdP

Let G (T, P2) or (T, P2) (T, P2) = (T, P1) + VmdP
P2 P1

Recall: Solid-Liquid Equil.

(T, P2) = (T, P1) + VmdP
P1 P2

Vm is small by approximation or we can say that the solid and liquids are (I) Meaning as you change the pressure, the volume does not change Vm is constant (good approx.)

Recall:1-component, 2-phase system

Component: water System: Ice + liquid water

dG = 0 ; dnice = dnliquid water (T, P2) = (T, P1) + Vm(P2 P1) (T, P2) = (T, P1) (T)

Summary
(T) The Gibbs Free Energy most of the time is just a function of temperature This is a close approximation And we can say that this is a good approximation

Recall: Ideal Gas

dG = -SdT + VdP ; Vm = RT/P dGm = VmdP (T,P1) = (T,P1) + RT/PdP = (T,P1) + RT ln P2/P1 We can reference this to the standard state. We can take P1 as 1 bar or 1 atm as our reference point
P2 P1

cont.
(T,P) = (T) + RT ln P = (T) + RT ln P/1atm/bar (T,P) = (T) + RT ln P

Any questions? Lets continue now with multicomponent systems

Recall:1-component, 2-phase system

Component: water System: Ice + liquid water

What we know? Species change They get destroyed while others get created

Examples
H2(g) + Cl2(g) = 2HCl2(g) 2H2(g) + O2(g) = 2H2O(l) H2O(l) H2O(s) or a cell place in a beaker of distilled water

G (T,P,n1,n2)
What if I change n1 and/or n2 dG = (G/T)P,n ,n dT + (G/P)T,n ,n dP + (G/n1)P,T,n dn1 + (G/n2)P,T,n dn2 (G/T)P,n ,n = ? (G/P)T,n ,n = ?
1 2

cont.
We will define the other 2 as (G/n1)P,T,n = 1 (G/n2)P,T,n = 2
2

Rewriting: SdT + VdP + idni

j i=1

cont.
G is extensive, scales with size of the system

= (G/ni)P,T,n
is intensive,

scales not with size of the system

n obviously scales with size of the system extensive

Summary
We can now define the other fundamental equations with
H = G + TS dH = dG + d(TS)

dH= TdS + VdP + idni

dU=TdS PdV dA=-SdT - PdV
i=1

dU= TdS PdV + idni

i=1

dA= SdT PdV + idni

i=1

Summary
We can also write in several ways:

dH= TdS + VdP + idni

i=1

i = (H/ni)S,P,n

dU= TdS PdV + idni

i=1

i = (U/n1)S,V,n

cont.
What do we want to prove?

ini = G or simply i = i This is our goal Anyone? or QUIZ? or HomeWork???

cont.
G (T,P,n1,n2) G (T,P,n1,n2) G (T,P, n1,n2) G(T,P,n1,n2) = G(T,P, n1,n2) deriving
(G/n1)(n1/) + (G/n2)(n2/) = G(T,P, n1,n2)

1 n1 + 2 n2 =

cont.

1 n1 + 2 n2 =
1 + 2 =

G
G

i ni = GT

Partial Molar Quantity a thermodynamic quantity indicates how an extensive property of a solution/mixture varies with changes in the molar composition of the mixture at constant temperature and pressure a partial derivative with respect to the quantity (number of moles) of the component of interest

Ex. Partial Molar Volume the partial molar volume of a substance X in a mixture is the change in volume per mole of X added to the mixture Ex. 1 mole of water added to a volume of water will increase the volume by 18 cm3 Ex. 1 mole of water added to a volume of ethanol will increase the volume by 14 cm3

Mole Fraction
a way of expressing composition of a mixture The mole fraction of each component i is defined as the amount of substance ni divided by the total amount of substance in the system n :

The sum of all the mole fraction is equal to 1:

n = ni
i

Xi = 1
i

Consider a mixture of A and B The mole fraction of A would be moles of A divided by the moles of A and moles of B:
mole fraction of A = moles of A moles of A + moles of B

or simply:
mole fraction of A = nA nA + nB

A mixture of A and B
Gas
A(g) B(g) YA YB = 1 - YA

P, T

Liquid

A(l)
B(l)

XA
XB = 1 - XA

Review
Considering the solution of A and B to be ideal Will it obey Raoults Law? What is the value of G of mixing A and B?

Recall: Raoults Law

So is P A = ? PTwhat = total pressure what is P PB = ? = PA + B PA* PA* = pressure P of T pure A PB PA
0

PB A = partial pressure of B A

PB* = pressure of pure B

1

XB

cont. Raoults Law

the vapor pressure of an ideal solution is dependent on the vapor pressure of each chemical component and the mole fraction of the component present in the solution
PA = XAPA*

cont. Raoults Law

At equilibrium, the total vapor pressure of an ideal solution is

P = XAPA* + XBPB* + P = XiPi*
i

What is the relation between P and YA

P= (PA*)(PB*)

(PA*) + (PB* PA*)(YA)

PA*

P PB PA

PB*

XB

Recall: 2-component system diagram

p=1 v=3 p=2 v=2

Vapor

Liq.+Vap.

p=1 v=3

Liquid
0 1

If we know the total P and T, can we plot it considering both mole fractions?
P= (PA*)(PB*)

PA*

(PA*) + (PB* PA*)(YA) Phases?

Liquid

Liq.+Gas

PB*
Gas
0 1

XB , Y B

Starting at P1 and lowering it to a point, P2 , what will be the relationship of XB and YB?
PA* P2 YB < XB YB(2) XB(2) (1) 1
Liquid
Liq.+Gas

P1 P2 PB*

Gas
0

XB , YB

lowering the pressure further

PA* P3

Liquid
Liq.+Gas

P2

P3 PB*

Gas
0

Y B < XB YB(3)
1

XB , YB

XB(3)

lowering the pressure further

PA*

Liquid
Liq.+Gas

P3 PB*
Gas
0

Y B = XB
1

XB , YB

lowering the pressure further

PA*

Liquid
Liq.+Gas

PB*
Gas
0

XB , YB

YB

Can you think of an application for this?

PA*
Liq.+Gas

Liquid

PB*
Gas
0

XB , Y B

How much of each component are there in each phase?

PA*
Liq.+Gas

Liquid

PB*
Gas
0 1

XB , Y B

cont.
nA nB ng nl = = = = total number of moles of A total number of moles of B total number of moles of gas total number of moles of liquid

nA = (YA)1(ng)1 = (YA)1(nTotal)

How much of each component are there in each phase?

nA = (YA)2(ng)2 + (XA)2(nl)2 = (YA)1 [(ng)2 + (nl)2 ]

PA*
Liquid
Liq.+Gas

PB*
Gas
0

XB , YB

cont.
nA = (YA)1(ng)1 = (YA)1(nTotal) nA = (YA)2(ng)2 + (XA)2(nl)2 = (YA)1 [(ng)2 + (nl)2 ]

How much of each component are there in each phase?

PA*
2
Liq.+Gas

Liquid

PB*
1 Gas
0 1

XB , Y B

cont. (YA)1(ng)2 + (YA)1(nl)2 = (YA)2(ng)2 + (XA)2(nl)2 [ (YA)1 (YA)2 ](ng)2 = [ (XA)2 (YA)1 ](nl)2 (ng)2 [ (XA)2 (YA)1 ] = (nl)2 [ (YA)1 (YA)2 ]
Lever Rule - How much of each component is there in each phase?

Consider a mixture of A and B

YA YB

A = gas phase B = liquid phase T = fixed

2 degrees of freedom P (T, T, XB )

XA XB

XB

Recall: Phase diagram for the mixture

Bubble Line PA*
Liq.+Gas

Liquid

PB* Dew Line

Gas
0 1

XB , Y B

Recall: Daltons & Raoults

So from And from Also from Raoults Daltons Law: Raoults Law: Law: PA = ? PA = ? PB = XBPB* = Y AP = XAPA* = (1 XA)PB* Rearranging: YA = PA /P = PA /(PA + PB) =

XAPA*
XAPA* + XBPB*

Recall: Daltons & Raoults

=
XAPA* XAPA* + (1 XA)PB*

XAPA*
XAPA* + PB* XAPB* XAPA* PB* + XA(PA* PB*)

Recall: Daltons & Raoults

YA =
XAPA* PB* XA(PB* + PA*) YAPB*

XA =

PA* + YA(PB* PA*) PA

YA P =

P =

XAPA*
YA

Summary
P =

PA*PB*
PA* + YA(PB* PA*)

Consider a mixture of A and B

YA YB

A = gas phase B = liquid phase P = fixed

2 degrees of freedom T (P, P, XB)

XA XB

XB

Recall: T vs X phase diagram

Dew Line T TA*
0

Vapor
Liq.+Vap.

TB*

Liquid

Bubble Line
1

XB

Recall: T vs X phase diagram

TB*

Vapor

T TA*
0

Liquid

YB

XB

XB

Consider a mixture of A and B

A = volatile solvent B = solute

Recall: P vs X plot
PA*
T = fixed PA* == Xpressure APA* = (1 of A XB) PA* What to remember? If the solution behave as plotted, then it is an _?_ solution.
1 0

0 1

XB XA

Consider a sugar solution

PA

PA* PA = PA* XAPA* = PA*(1 XA) = PAXB

Recall: H2O phase diagram

1 atm

273

373

Problem 2.1
Ten grams of pure sodium chloride is dissolved in 1000 g of water. By how much is the freezing temperature depressed from its normal melting temperature of T = 273.15 K? (Kf = 1.86 K kg mol1).

Problem 2.1
Ten grams of pure sodium chloride is dissolved in 1000 g of water. By how much is the freezing temperature depressed from its normal melting temperature of T = 273.15 K? (Kf = 1.86 K kg mol1).

T = 1.86 x 1000 x 0.01/58.5 T = 0.32 K

Adding salt to water

Adding salt to water

Adding salt to the water has caused both the lines to drop down the page, thus causing the intersection temperature to change. Adding salt to water, in addition to changing its chemical potential, changes the temperature at which boiling occurs boiling temperature is raised, relative to that of pure water.

Recall: Freezing Point Depression

FPpure solvent > FPsolution

conc. of nonvolatile solute, change in FP

TFP = Kfm
where T = FPsolvent FPsoln Kf = molal FP depression constant m = molal concentration of solute

Recall: Boiling Point Elevation

BPpure solvent < BPsolution

conc. of nonvolatile solute, change in BP

TBP = Kbm
where T = BPsoln BPsolvent Kb = molal BP elevation constant m = molal concentration of solute

Problem 2.2
Predict the BP of 1.25 m sucrose solution. (Kb of H2O = 0.512 oC/m)

BPsoln = (0.512 x 1.25) + 100 C T = 100.64 C

?Question? / Point to ponder Why do we prefer molaLity m to molaRity M in solving boiling point elevation and freezing point depression?
We prefer m because the volume of the liquid or solution changes with temperature, whereas that of a mass does not Molality is temperature independent whereas concentration is not

Recall: Vapor Pressure Lowering

VPpure solvent > VPsolution

conc. of solute, change in VP

P = XsoluteVPsolvent
where P = VPpure solvent VPsolution Xsolute = mole fraction of solute VPsolvent = VP of pure solvent

Problem 2.3
Calculate the vapor pressure of a 2.0 M aqueous solution of sucrose (342.3 g/mol) at 30 oC. Vapor pressure of pure water at 30 C is 31.82 mm Hg. (water = 0.99565 g/mL)

Problem 2.3
Calculate the vapor pressure of a 2.0 M aqueous solution of sucrose (342.3 g/mol) at 30 oC. Vapor pressure of pure water at 30 C is 31.82 mm Hg. (water = 0.99565 g/mL)

P = 0.9651 x 31.82 P = 30.72 mm Hg

Recall: Osmotic Pressure

= nRT/V
= MRT
where = osmotic pressure n = moles of solute M = molarity of solution R = gas law constant T = absolute temperature

Problem 2.4
The average osmotic pressure of seawater is about 30.0 atm at 25 oC. Calculate the molar concentration of an aqueous solution of sucrose (C12H22O11) that has the same osmotic pressure with seawater.

Problem 2.4
The average osmotic pressure of seawater is about 30.0 atm at 25 oC. Calculate the molar concentration of an aqueous solution of sucrose (C12H22O11) that has the same osmotic pressure with seawater.

M = 30 / (0.0821 x 298.15) M = 1.23 M

Definition of Terms
Cryoscopy
measurement of the degree of

dissociation or molar mass of solute using freezing point depression data comes from Greek kryos meaning frost

Ebullioscopy
measurement of molar mass of solute

using boiling point elevation data from the Latin (e)bullire meaning bubbly

Recall: T plot
also recall:

cont.

cont.
and at constant T and P, assuming an ideal mixture, we can relate this to the mole fraction of the component/solute:

?Question?

Who said that the amount of

gas dissolved in a liquid or solid is in direct proportion to the partial pressure of the gas?

William Henry

Henrys Law

At a constant temperature, the amount of a given gas dissolved in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.

Ideal Dilute Solutions

In an ideal dilute solution, the solvent obeys Raoults law but the solute obeys Henrys law.

Henrys Law

P = KHc
where P = partial pressure of the solute above the solution KH = Henrys law constant (L-atm/mol) c = molar concentration of solute

Henrys Law

P = KHX
where P = partial pressure of the solute above the solution KH = Henrys law constant (atm) X = mole fraction of the solute

Henrys Law

c = KHP
where P = partial pressure of the solute above the solution KH = Henrys law constant (mol/L-atm) c = molar concentration of solute

cont.
again recall the chemical potential, assuming an ideal dilute mixture at constant T and P, we can replace the mole fraction:

KH m c P* m c

Problem 2.5
What is the concentration of molecular oxygen in water at 25 C? The atmosphere above the water has a pressure of 105 Pa and contains 21% of oxygen. KH O = 1.28 103 mol/L-atm
2

Problem 2.5
What is the concentration of molecular oxygen in water at 25 C? The atmosphere above the water has a pressure of 105 Pa and contains 21% of oxygen. KH O2 = 1.28 103

PO = 0.21 x 105
2

= 2.1 x 104 = 0.21 atm

[O2] = 0.21 x (1.28 x 103) = 2.69 x 104 M

Consider a liquid A and liquid B

A
Recall if we have pure A: A*(l,T,P) = A(g,T) + RT ln PA/P At coexistence, we have: A(l,T,P) = A(g,T,PA)

Considering them ideal: A(g,T,PA) = A(g,T) + RT ln PA/P : A(l,T,PA) = A(g,T) + RT ln PA/P

Summary
We will have a convenient form of A in an ideal liquid mixture:

A(l,T,P) = A*(l,T,P) + RT ln PA/P*

Recall Raoults Law

A(l,T,P) = A*(l,T,P) + RT ln XA

Summary

A(l,T,P) = A*(l,T,P) + RT ln XA

XA = 0 1

of pure liquid

Summary
The chemical potential of the liquid in the solution, A is always less than that of the pure liquid A* at the same temperature, T and pressure, P. Implications of this is clearly demonstrated in osmotic pressure

Consider a liquid A and liquid B

A

Liquid mixture of A and B

A + B
Recall G: G = nXAA + nXBB Recall A: G = nXA(A* + RT ln XA) + nXB(B* + RT ln XB)

Rearranging: Gmix= nRT (XAlnXA + XBlnXB)

Summary
Gmix= nRT (XAlnXA + XBlnXB) The G of mixing of the liquid is similar to that of a gas There is no interaction between the particles of the mixture Therefore we can say that entropy contributes to the mixing

Recall: G = VdP + SdT

Smix = -[(Gmix)/T]P = - nR(XAlnXA + XBlnXB) Hmix = Gmix + TSmix =0 Vmix = -[(Gmix)/P]T =0

Summary
The H of mixing of the liquid is negligible since there is no interaction between the particles Similarly Vmixing is also zero due to the fact that in an ideal solution there will be no interaction between the components particles.

Consider a liquid A and liquid B

A
For a non ideal liquid A: A*(l,T,P) < 0 We have an interaction between particles of A A- - -A AA < 0 Similarly we have an interaction between B B---B BB < 0

Liquid mixture of A and B

A + B
Mixing: A --- B A --- B
AB AB

Now we have 2 : AB + AB
If we take also the first interactions: mix= 2AB (AA +BB)

 = 2AB (AA +BB) The possible values of is

either negative or positive We can say now that there is an energy of mixing unlike in the ideal mixture. If its positive, then the interaction between like particles are favorable

Positive deviation: > 0

Hmix Vmix Gmix = n/4 () + nRT (XAlnXA + XBlnXB) Gmix(non-ideal) > Gmix(ideal) ex. acetone and carbon disulfide

Problem 2.6
Given two liquids, A and B. A being carbon disulfide and B acetone. If the liquids are mix together and the mixture is not ideal, draw a phase diagram showing the relationship between P and composition of the mixture. (Note: use dotted line
for non-ideal, straight line for ideal)

CS2 : b.p. = 319 K C3H6O : b.p. = 330 K

PA* P PB PA
0

PAcetone*

XB

CS2:C3H6O mixture
PC3H6O> XC3H6OP*C3H6O P*CS
2

PCS2 > XCS2P*CS2

PT(n.i.) > PT(ideal)

P*C H O
3 6

XC H O
3 6

Negative deviation: < 0

Gmix(non-ideal) < Gmix(ideal) Unlike in the positive deviation, the interaction between dissimilar species is favorable. ex. acetone and chloroform

Negative deviation: < 0

H3C H3C
For a non ideal liquid mixture like acetone and chloroform, H-bonding exist. Theres an interaction H between different species.

O C=O

The species will prefer to be in the liquid phase rather than in the gas.

CCl

Cl

Cl

Simply, mixing is favorable.

CHCl3 : b.p. = 335 K C3H6O : b.p. = 330 K

P*C3H6O

P*CHCl3

XCHCl3

CHCl3:C3H6O mixture
PC3H6O< XC3H6OP*C3H6O P*C3H6O PCHCl3< XCHCl3P*CHCl3

PT(n.i.) < PT(ideal)

P*CHCl3

XB

Recall: Ideal Dilute Solutions

XCS2 = XB 1

P*CS = P*B
2

P*C H O
3 6

XCS2 = XB 0

XCS = XB
2

Recall: Ideal Dilute Solutions

Case 2: XB 0 PB = XBKB obeys Henrys Case 1: XB 1 PB = XBP*B obeys Raoults

P*B P*A

XB

Problem 2.7
Benzene and toluene form an ideal mixture, i.e. they obey Raoults law. At 20 C, the pressure of benzene and toluene are 0.747 and 0.223 of their partial pressure respectively. What is the pressure above a mixture of these two liquids that contains 12 mol% of benzene?

Problem 2.8
Given a liquid mixture of A and B at 50 C. What is the composition of B in the gas phase if the molar fraction of A in the liquid phase is 0.9 and the vapor pressures of pure A and pure B are 0.67 bar and 1.2 bar respectively.

+ deviation, azeotrope

 deviation, azeotrope

Summary
Recall the 4 colligative properties nsolvent >>> nsolute

A(l,T,P) < A*(l,T,P) A(l,T,P) = A(g,T,P)

You can derive the equation of the 4 properties from the chemical potential

Summary
Lets consider vapor pressure lowering P = PA PA* = XAPA* PA* = PA*(XA 1) = (1 XA)PA* = (XBPA*) <0

Summary
How about boiling point elevation? A(l,T,P) = A(g,T,P)
obeys Raoults law

A*(l,T,P) + RT ln XA
solute is nonvolatile

= A*(g,T,P) A*(l,T,P) + RT ln XA = A*(g,T,P)

Summary
Rearranging: ln XA = 1/RT [ A*(g) A*(l) ]
vaporization

ln XA = Gvap / RT we do not want the log/ln we do want a T not just the T

Summary
Simplify ln XA in terms of solute: ln XA = ln (1 XB)
solute, small amt.

we

= = = also

XB nB / n A + n B nB / n A need m (molality) so

Summary
We multiply the n with M (mass): (nB / nA) (MA/MA)
nB/MA = molality MA/nA = molar mass

= (mB)(MMA) going back to our previous eq. (mB)(MMA) = Gvap / RT mB = Gvap / RT(MMA)

Summary we eliminated the log, but still no delta T how do we get that? remember, everything is very small so one thing to get a very small change in T is to get the derivative with respect to T so take the derivative of both side with respect to T

Summary
/T [ mB = Gvap / RT(MMA) ] (mB/T)P = [1/R(MMA)] [(Gvap/T) /T]P Recall the Gibbs-Helmholtz eq.

incorporating that to the previous eq.

Summary
(G/T)/T = H/T (mB/T)P = Hvap/T2R(MMA) rewriting dT = (T2R(MMA)/Hvap) dmB since we are putting small amounts of solute B, dmB = mB + 0 rewriting dT = (T2R(MMA)/Hvap) mB

Summary
dT = (T2R(MMA)/Hvap) mB rewriting T =

Tb2R(MMA)
Hvap

mB

T = KB mB

Historical background
Fragrant eau de Cologne is a dilute perfume introduced in Cologne (Germany) in 1709 by Jean Marie Farina. The word perfume comes from the Latin per fumem, meaning through smoke. It was probably a modification of a popular formula made before 1700 by Paul Feminis, an Italian in Cologne, and was based on bergamot and other citrus oils. The water of Cologne was believed to have the power to ward off bubonic plague.

cont.
Eau de Cologne perfume is made from about 8085 per cent water and 1215 per cent ethanol. Volatile esters make up the remainder, and provide both the smell and colour. These esters are stable in the dark, butdegrade in strong sunlight, which explains why so many perfumes are sold in bottles of darkened or frosted glass.

Changing the perceived concentration

Adding alcohol to an aqueous perfume increases the pressure of the gases above the liquid. WHY? The vapor pressure of alcohol is higher than that of water. What can we say in terms of the activities of the components?

Changing the perceived concentration

We can say that the activity, a, of the organic components imparting the smell will increase. This increases the perceived concentration of the esters. And increasing a(ester) has the effect of making the cologne more pungent.

Changing the perceived concentration

So what? The product requires less ester because the alcohol increases its perceived concentration. Incidentally, the manufacturer will save money this way. NOTE: Essential oils are very expensive.

Thermodynamic activity, a
The concept of activity was introduced in the early 20th century by G. N. Lewis. The values of activity, a, and concentration [c ] are the same for very dilute solutions, so the ratio of a and c is one because the real and perceived concentrations are the same.

Thermodynamic activity, a
As a working definition, the activity may be said to be the perceived concentration and is therefore somewhat of a fudge factor. But more formally, the activity a is defined by:

Thermodynamic activity, a

The activity a and the activity coefficient are both dimensionless quantities, which explains why we must include the additional c term, thereby ensuring that a also has no units.

Thermodynamic activity, a

where

a = activity = activity coefficient c = concentration c = 1M

Problem 2.9
A tooth filling is made of a silver amalgam that comprises 37 mol % silver. What is the activity of the mercury, a(Hg)?
Note: The word amalgam comes from the Greek malagma meaning to make soft, because a metal becomes pliable when dissolved in mercury. Another English word from the same root ismalleable.

Problem 2.9
X(Hg) + X(Ag) = 1 X(Hg) = 1 X(Ag) = 0.63

And since, the activity of the mercury a(Hg) is the same as its mole fraction, X(Hg),
X(Hg) = a(Hg) = 0.63

Problem 2.10
Hydrogen gas is mixed with a nitrogen bath gas. The overall pressure is P . If the mole fraction of the hydrogen is expressed as 10 per cent, what is its activity?
Note: The activity of a pure gas is its pressure in multiples of the total pressure, P.

Problem 2.10
10% = 0.1 ; P = 1 By definition, X(X) = partial pressure, P(X), so: a(H2) = = = = X(H2) P(H2) P 0.1/1 0.1

Activity of solutions

We can consider several situations:

The activity of a liquid mixture or mixture of

liquids. The activity of solute in a solvent. The activity of ions in a solution.

Not a good idea to suggest that the activity of a liquid in a mixture is equal to its mole fraction X because of complications due to intermolecular interactions

Activity of solutions

The activity a and concentration c may be considered to be wholly identical if the concentration is tiny. For all these other situations, we will employ the Debye Hckel laws to calculate the activity coefficient .

Activity of solutions

Knowing the value of , we then say that a = (c c ) Remember to remove the concentration units because a is dimensionless. DebyeHckel theory is derived from the knowledge of electrostatic considerations

DebyeHckel
The DebyeHckel theory suggests that the probability of finding ions of the opposite charge within the ionic atmosphere increases with increasing attractive force.

Ionic interactions
We assume the ions have an energy distribution as defined by the Boltzmann distribution law. We can say that electrostatic forces affect the behavior and the mean positions of all ions in solution Larger-charge ions are more likely to associate strongly than ions having a smaller charge

Recall: Maxwell-Boltzmann law

The thermodynamic temperature is the sole requirement to describe it. Molecules do not have the same energies but a distribution of energies. It shows few particles having large and tiny energies while majority possesses lesser energies.

Energy distribution of N2

Electrostatic interaction

Electrostatic interaction

where

= electrostatic interaction z+, z = magnitude ionic charge r = inter-ionic distance = relative permittivity

Ternary system
C = components =3

F =5P

Gibbs-Roozeboom diagram
A AB
A, B & C represents pure substances

AC
edges represents binary systems

BC

Gibbs-Roozeboom diagram
A
XA + X B + X C = 1 A point inside the triangle represents a ternary systems

AB & AC : miscible ; BC : partially miscible Partially Miscible Liquids

plait point the point in which compositions of 2 phases in equilibrium plait point becomes identical

b & c represents B-rich and C-rich phases respectively that are at equilibrium bc tie line

d1 d2 represents a composition of Brich layer d2

b d1

P=1
c

d2 d3 represents a composition of Crich layer d3

P=2

Partially Miscible Liquids

A
b & c represents B-rich and C-rich phases respectively that are at equilibrium bc tie line

P=1
c b

P=2

CH3COOH-CHCl3-H2O

Further readings
Common Ion Effects Double Salt Formation Salting Out