Simple Mixtures

Physical Chemistry II
Dr. ir. Jerome B. Taboada

Simple Mixtures

Restrictions
Binary Mixtures
xA + xB = 1, where xA = fraction of A
Non-Electrolyte Solutions
Solute not present as ions

Partial Molar Quantities -Volume

Partial molar volume of a

substance slope of the variation of
the total volume plotted against the
composition of the substance
Vary with composition
due to changing molecular
environment
VJ = (V/ nJ) p,T,n
pressure, Temperature and
amount of other
component constant

Partial Molar Volumes

Water & Ethanol

Partial Molar Quantities & Volume

If the composition of a mixture is changed by addition of dnA and dnB

dV = (V/ nA) p,T,nA dnA + (V/ nB) p,T,nB dnB
dV =VAdnA + VBdnB
At a given compositon and temperature, the total volume, V, is
V = nAVA + nBVB

Measuring Partial Molar Volumes

For NaCl the volume of solution from 1 kg of water is:
V= 1003 + 16.62b + 1.77b1.5 + 0.12b2

What are the partial molar volumes?

VNaCl = (V/nNaCl) = (V/nb) = 16.62 + (1.77 x 1.5)b0.5 + (0.12 x 2) b1
At b =0.1, nNaCl = 0.1

VNaCl = 16.62 + 2.655b0.5 + 0.24b = 17.48 cm3 /mol

V = 1004.7 cm3
nwater = 1000g/(18 g/mol) = 55.6 mol

V = nNaClVNaCl + nwaterVwater
Vwater = (V - VNaCl nNaClr )/ nwater = (1004.7 -1.75)/55.6= 18.04 cm3 /mol

Partial Molar Quantities - General

Any extensive state function can

have a partial molar quantity
Extensive property depends on
the amount of a substance
State function depends only on
the initial and final states not on
history
Partial molar quantity of any
function is just the slope (derivative)
of the function with respect to the
amount of substance at a particular
composition
For Gibbs energy this slope is
called the chemical potential,

Partial Molar Free Energies

Chemical potential, J, is defined as the partial molar Gibbs energy @

constant P, T and other components
J = (G/ nJ) p,T,n
For a system of two components: G = nAA + n B B
G is a function of p,T and composition
For an open system constant composition,
dG =Vdp - SdT + A dnA + B dn B
Fundamental Equation of Thermodynamics
@ constant P and T this becomes, dG = A dnA + B dn B
dG is the the non expansion work, dwmax
changing composition can result in work, e.g. an
electrochemical cell

Chemical Potential

Gibbs energy, G, is related to the internal energy, U

U = G - pV + TS (G = U + pV - TS)
For an infinitesimal change in energy, dU
dU = -pdV - Vdp + TdS + SdT + dG
but
dG =Vdp - SdT + A dnA + B dn B
so
dU = -pdV - Vdp +TdS +SdT + Vdp - SdT + A dnA + B dn B
dU = -pdV + TdS + A dnA + B dn B
at constant V and S,
dU = A dnA + B dn B or J = (U/ nJ)S,V,n

 and Other Thermodynamic Properties

Enthalpy, H (G = H - TS)
dH = dG + TdS + SdT
dH= (Vdp - SdT + A dnA + B dn B) - TdS + SdT
dH = VdP - TdS + A dnA + B dn B
at const. P & S :
dH = A dnA + B dn B or J = (H/ nJ)p,T,n
Helmholz Energy, A (A = U-TS)
dA = dU - TdS - SdT
dA = (-pdV + TdS + A dnA + B dn B ) - TdS - SdT
dA = -pdV - SdT + A dnA + B dn B
at const. V & T :
dA = A dnA + B dn B or J = (A/ nJ)V,T,n

Gibbs-Duhem Equation

Recall, for a system of two components:

G = nAA + n B B

If compositions change infinitesimally

dG = A dnA + B dn B + nAdA + n Bd B

But at constant p & T, dG = A dnA + B dn B so

A dnA + B dn B = A dnA + B dn B + nAdA + n Bd B
or
nAdA + n Bd B = 0

For J components,

nidi = 0 (i=1,J) {Gibbs-Duhem Equation}

Significance of Gibbs-Duhem

Chemical potentials of multi-component systems cannot

change independently
Two components, G-D says, nAdA + n Bd B = 0
means that d B = -(nA/ n B)dA
Applies to all partial molar quantities
Partial molar volume dVB = -(nA/ n B)dVA
Can use this to determine on partial molar volume from
another
See example next slide

Example: Using the Gibbs-Duhem equation (1 of 2)

Example: Using the Gibbs-Duhem equation (1 of 2)

Example: Using the Gibbs-Duhem equation (2 of 2)

Thermodynamics of Mixing

For 2 Gases (A &B) in two containers, the Gibbs

energy, Gi
Gi = nAA + nBB
But = + RTln(p/p)
Gi = nA(A + RTln(p/p) )+ nB(B + RTln(p/p))
If p is redefined as the pressure relative to p
Gi = nA(A + RTln(p) )+ nB(B + RTln(p) )
After mixing, p = pA + pB and
Gf = nA(A + RTln(pA) )+ nB(B + RTln(pB) )
So Gmix = Gf - Gi = nA (RTln(pA/p) )+ nB(RTln(pB /p)
Replacing nJ by xJn and pJ/p=xJ (from Daltons Law)
Gmix = nRT(xA ln (xA ) + xBln(xB ))
This equation tells you change in Gibbs energy
is negative since mole fractions are always <1

is the standard chemical potential of a pure gas at 1 bar (p)

Gibbs Energy of Mixing

Of
Two Ideal Gases

Example: Calculating the Gibbs Energy of Mixing

Entropy and Enthalpy of Mixing

For Smix, recall G = H - TS

Therefore Smix = -Gmix / T
Smix = - [ nRT(xA ln (xA ) + xBln(xB ))] / T
Smix = - nR(xA ln (xA ) + xBln(xB )
It follows that Smix is always (+) since
xJln(xJ ) is always (-)
For Hmix
H = G + TS ={nRT(xA ln (xA ) + xBln(xB )}
+T{- nR(xA ln (xA ) + xBln(xB )}
H ={nRT(xA ln (xA ) + xBln(xB )} {nRT(xA ln (xA ) + xBln(xB )}
H = 0
Thus driving force for mixing comes from
entropy change

Entropy of Mixing
Two Ideal Gases

Chemical Potentials of Liquids

Ideal Solutions
Note: superscript * denotes pure substances

At equilibrium: A(l) = A(g)

For pure liquid, *A(l) = A + RT ln(p *A) [1]
For A in solution, A(l) = A + RT ln(p A) [2]
Subtracing [1] from [2] :
A(l) - *A(l) = RT ln(pA) + RT ln(p *A)
A(l) - *A(l) = RT{ln(pA) - ln(p *A)}
= RT{ln(pA/p *A)}
A(l) = *A(l) + RT{ln(pA/p *A)}

[3]

Raoults Law - ratio of the partial pressure of a component of a mixture to its

vapor pressure as a pure substance (pA/p*A) approximately equals the mole
fraction, xA
pA = xA p*A

Combining Raoults law with [3] gives

A(l) = *A(l) + RT{ln(xA)}

Ideal Solutions/Raoults Law

p*
B
Total Pressure

Pressure

p*
A

Partial
Pressure of B

Partial
Pressure of A
Mole Fraction of A, x

Mixtures which obey Raoults

Law throughout the
composition range are Ideal
Solutions
Phenomenology of Raoults
Law: 2nd component inhibits
the rate of molecules leaving a
solution, but not returning
rate of vaporization XA
rate of condensation pA
at equilibrium rates equal
implies pA = XA p*A

Deviations from Raoults Law

Raoults Law works well when components of a

mixture are structurally similar
Wide deviations possible for dissimilar mixtures
Ideal-Dilute Solutions
Henrys Law (William Henry)
For dilute solutions, v.p. of solute is
proportional to the mole fraction (Raoults
Law) but v.p. of the pure substance is not the
constant of proportionality
Empirical constant, K, has dimensions of
pressure
pB = xBKB (Raoults Law says pB = xBpB)
Mixtures in which the solute obeys Henrys Law
and solvent obeys Raoults Law are called Ideal
Dilute Solutions
Differences arise because, in dilute soln, solute
is in a very different molecular environment
than when it is pure

Applying Henrys Law & Raoults Law

Henrys law applies to the

solute in ideal dilute
solutions
Raoults law applies to
solvent in ideal dilute
solutions and solute &
solvent in ideal solutions
Real systems can (and do )
deviate from both

Applying Henrys Law

What is the mole fraction of dissolved hydrogen dissolved

in water if the over-pressure is 100 atmospheres?
Henrys constant for hydrogen is 5.34 x 107
PH2= xH2K; xH2 = PH2 /K= 100 atm x 760 Torr/atm/ 5.34 x
107
xH2 = 1.42 x 10-3
In fact hydrogen is very soluble in water compared to other
gases, while there is little difference between solubility in
non-polar solvents. If the solubility depends on the
attraction between solute and solvent, what does this say
about H2 -water interactions?

Properties of Solutions

For Ideal Liquid Mixtures

As for gases the ideal Gibbs energy of mixing is
Gmix = nRT(xA ln (xA ) + xBRTln(xB ))
Similarly, the entropy of mixing is
Smix = - nR(xA ln (xA ) + xBln(xB )
and Hmix is zero
Ideality in a liquid (unlike gas) means that interactions are
the same between molecules regardless of whether they are
solvent or solute
In ideal gases, the interactions are zero

Real Solutions

In real solutions, interactions between different molecules are different

May be an enthalpy change
May be an additional contribution to entropy (+ or - ) due to arrangement of
molecules
Therefore Gibbs energy of mixing could be +
Liquids would separate spontaneously (immiscible)
Could be temperature dependent (partially miscible)
Thermodynamic properties of real solns expressed in terms of ideal solutions using
excess functions
Entropy: SE = Smix - Smixideal
Enthalpy: HE = Smix(because Hmixideal = 0)
Assume HE = nbRTxAxB
where is const. b =w/RT
w is related to the energy of AB interactions relative to AA and BB
interactions
b> 0, mixing endothermic; b< 0, mixing exothermic solvent-solute
interactions more favorable than solvent-solvent or solute-solute
interactions
Regular solution is one in which HE 0 but SE 0
Random distribution of molecules but different energies of interactions
GE = HE

Gmix = nRT{(xA ln (xA ) + xBRTln(xB )) + bRTxAxB

(Ideal Portion
+ Excess)

Activities of Regular Solutions

Recall the activity of a compound, a, is defined

a = gx
where g = activity coefficient
For binary mixture, A and B, consideration of excess
Gibbs energy leads to the following relationships
(Margules eqns)
ln gA = bxB2 and ln gB = bxA2
[1]

As xB approaches 0, gA approaches 1

Since, aA = gAxA, from [1]

a A xAe

bx 2B

But, aA

x Ae

b 1 x 2A

pA
p *A

p A pressure pure A

so
b 1 x 2A
p*A
p A
x
e
A

If b = 0, this is Raoults Law

If b < 0 (endothermic mixing),
gives vapor pressures lower than
ideal
If b > 0 (exothermic mixing), gives
vapor pressures higher than ideal
If xA<<1, becomes pA = xA eb pA*

Henrys law with K = eb pA*

Colligative Properties of Dilute

Solutions

Colligative Properties

Properties of solutions which depend upon the number

rater than the kind of solute particles
Arise from entropy considerations
Pure liquid entropy is higher in the gas than for the
liquid
Presence of solute increases entropy in the liquid
(disorder increases)
Lowers the difference in entropy between gas
and liquid hence the vapor pressure of the liquid
Result is a lowering chemical potential of the solvent
Types of colligative properties
Boiling Point Elevation
Freezing Point Depression
Osmotic pressure

Colligative Properties - General

Assumptions
Solute not volatile
Pure solute separates when
frozen
When you add solute the chemical
potential, A becomes
A = A * + RT ln(xA) where
A * = Chemical Potential of
Pure Substance
x A = mole fraction of the
solvent
Since ln(xA) in negative A < A*
Thus a reduction of chemical
potential

Boiling Point Elevation

At equilibrium (gas) = (liquid) or A(g) = A *(l) + RTln(xA)
Rearranging,(A(g) - A *(l))/RT = ln(xA) = ln(1- xB)
But , (A(g) - A *(l)) = G vaporization so
ln(1- xB) = G vap. /RT
Substituting for G vap. (H vap. -T S vap. )
{Ingnore T dependence of H & S}
ln(1- xB) = (H vap. -T S vap.)/RT = (H vap. /RT) - S vap./R
When xB = 0 (pure liquid A), ln(1) = (H vap. /RTb) - S vap./R = 0 or
H vap. /RTb = S vap./R where Tb= boiling point
Thus ln(1- xB) = (H vap. /RT) - H vap. /RTb = (H vap. /R)(1/T- 1/Tb)
If 1>> xB, (H vap. /R)(1/T- 1/Tb) - xB and if T Tb and T= T Tb
Then (1/T- 1/Tb) = T/Tb2 and (H vap./R) T/Tb2 = - xB so
T= - xB Tb2 /(H vap./R) or T= - xB Kb where Kb = Tb2 /(H vap./R)

Boiling Point Elevation

Kb is the ebullioscopic constant

Depends on solvent not solute
Largest values are for solvents with high boiling points
Water (Tb = 100C) Kb = 0.51 K/mol kg -1
Acetic Acid (Tb = 118.1C) Kb = 2.93 K/mol kg -1
Benzene (Tb = 80.2C) Kb = 2.53 K/mol kg-1
Phenol (Tb = 182C) Kb = 3.04 K/mol kg -1

Freezing Point Depression

Derivation the same as for boiling point elevation except

At equilibrium (solid) = (solid) or A(g) = A *(l) +
RTln(xA)
Instead of the heat of vaporization, we have heat of
fusion
Thus, T= - xB Kf where Kf = Tf2 /(H fus./R)
Kf is the cryoscopic constant
Water (Tf = 0C) Kf = 1.86 K/mol kg -1
Acetic Acid (Tf = 17C) Kf = 3.9 K/mol kg -1
Benzene (Tf = 5.4C) Kf = 5.12 K/mol kg-1
Phenol (Tf = 43C) Kf = 7.27 K/mol kg -1
Again property depends on solvent not solute

Temperature Dependence of Solubility

Not strictly speaking colligative property but can be

estimated assuming it is
Starting point the same - assume @ equilibrium is equal
for two states
First state is solid solute, B(s)
Second state is dissolved solute, B(l)
B(l) = B*(l) + RT ln xB
At equilibrium, B(s) = B(l)
B(s) = B*(l) + RT ln xB
Same as expression for freezing point except that use xB
instead of xA

Temperature Dependence of Solubility

To calculate functional form of temperature dependence you solve for mole

fraction
ln xB = [B(s) - B*(l)]/ RT = -G fusion/RT = -[H fus-T S fus]/RT
ln xB = -[H fus-T S fus]/RT = -[H fus /RT] + [S fus/R] {1}
At the melting point of the solute, Tm, G fusion/RTm = 0 because G fusion = 0
So [H fus-Tm S fus]/RTm = 0 or [H fus /RTm] -[S fus/R] = 0
Substituting into {1}, ln xB = -[H fus /RT] + [S fus/R]+ [H fus /RTm]
-[S fus/R]
This becomes ln xB = -[H fus /RT] + [H fus /RTm]
Or ln xB = -[H fus /R] [1/T - 1/Tm]
Factoring Tm, ln xB = [H fus /R Tm] [1 - (Tm /T)]
Or xB = exp[H fus /R Tm] [1 - (Tm /T)-1]
The details of the equation are not as important as functional form
Solubility is lowered as temperature is lowered from melting point
Solutes with high melting points and large enthalpies of fusion have low
solubility
Note does not account for differences in solvent - serious omission

Osmotic pressure

J. A. Nollet (1748) - wine spirits in tube with animal bladder

immersed in pure water
Semi-permiable membrane - water passes through into the tube
Tube swells , sometimes bladder bursts
Increased pressure called osmotic pressure from Greek word
meaning impulse
W. Pfeffer (1887) -quantitative study of osmotic pressure
Membranes consisted of colloidal cupric ferrocyanide
Later work performed by applying external pressure to balance the
osmotic pressure
Osmotic pressure , , is the pressure which must be applied to solution
to stop the influx of solvent

Osmotic Pressure vant Hoff Equation

J. H. vant Hoff (1885) - In dilute solutions the osmotic pressure obeys the
relationship, V=nBRT
nB/V = [B] {molar concentration of B, so =[B] RT
Derivation- at equilibrium solvent is the same on both sides of membrane: A
*(p) = A (x A,p +) {1}
A (x A,p +) = *A (x A,p +) + RTln(x A) {2}
p +
*A (x A,p +) = A *(p) + p
Vm dp {3} [Vm = molar volume of the
pure solvent]
p +
Combining {1} and {2} : A *(p) = A *(p) + p
Vm dp + RTln(x A)
For dilute solutions, ln(x A) = ln(x B) - x B
Also if the pressure range of integration is small,
p +
p +
p
V m dp = Vmp
dp = Vm
So 0 = V m + RT - x B or Vm= RT x B
Now nA V m = V and, if solution dilute x B - n B /nA so =[B] RT
Non-ideality use a virial expansion

=[B] RT{1 + B[B] + ...} where B I s the osmotic virial coef. (like
pressure)

Application of Osmotic Pressure

Determine molar mass of macromolecules

=[B] RT{1 + B[B] + ...} but [B] = c/M

where c is the concentration and M the
molar mass so

= c/M RT{1 + Bc/M + ...}

g h = c/M RT{1 + Bc/M + ...}

h/c = RT/(Mg) {1 + Bc/M + ...}
2
h/c = RT/(Mg) + RTB/(M g) + ...}
Plot of h/c vs. c has intercept of RT/(Mg) so

Intercept= RT/(Mg) or M= RT/(intercept

xg)

Units (SI) are kg/mol typical Dalton (Da)

{1Da = 1g/ mol}

Non-Ideality & Activities

Solvents

Recall for ideal solution A =A * + RTln(xA)

A* is pure liquid at 1 bar when xA =1

If solution does not ideal xA can be replaced with activity
aA
activtiy is an effective mole fraction
aA = pA/pA* {ratio of vapor pressures}
Because for all solns A =A * + RTln(pA/
p*A)
As xA-> 1, aA -> xA so define activity
coefficient,g, such that
aA = g A xA
As xA-> 1, gA -> 1
Thus A =A * + RTln(xA) + RTln(gA) {substiuting for a A}

Non-Ideality & Activities

Solutes (Ideal & Non-Ideal)

For ideal dilute solutions Henrys Law ( pB = KBxB) applies

Chemical potential B = B * + RTln(pB /pB*)
B = B * + RTln(KBxB /pB*) = B * + RTln(KB/pB*) +
RTln(xB )
KB and pB* are characteristics of the solute so you
can combine them with B *
B = B * + RTln(KBxB /pB*)

Thus B = B + RTln(xB )
Non-ideal solutes
As with solvents introduce acitvity and activity
coefficient
aB = pB/KB*; aB = g B xB
As xA-> 0, aA -> xA and gA -> 1

Activities in Molalities

For dilute solutions x B n B /nA , and x B = b/b

kappa, , is a dimensionless constant

For ideal-dilute solution, B = B + RTln(xB ) so B =

B + RTln( b/b) = B + RTln() + RTln( b/b)

Dropping b and combing 1st 2 terms, B = B+ RTln( b)

B = B+ RTln()

B has the standard value (B ) when b=b

As b ->0, B ->infinity so dilution stabilizes system
Difficult to remove last traces of solute from a soln
Deviations from ideality can be accounted for by defining
an activity aB and activity,g B,
aB = g B bB/b where g B ->1, bB -> 0
The chemical potential then becomes = + RTln( a)