Chapter 7: Simple Mixtures

Homework:

Exercises(a only):7.4, 5,10, 11, 12, 17, 21

Problems: 1, 8
Chapter 7 - Simple Mixtures
4 Restrictions
» Binary Mixtures
xA + xB = 1, where xA = fraction of A
» Non-Electrolyte Solutions
Solute not present as ions
 Partial Molar Quantities -Volume
4 Partial molar volume of a
ð
 


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 = (áV/ ánJ) p,T,n¶
pressure, Temperature and
amount of other component
constant
 Partial Molar Quantities & Volume
4 If the composition of a mixture is changed by addition of dnA and dnB
» dV = (áV/ ánA) p,T,nA dnA + (áV/ ánB) p,T,nB dnB
» dV =VAdnA + VBdnB
4 At a given compositon and temperature, the total volume, V, is
» V = nAVA + nBVB
 Measuring Partial Molar Volumes
4 Measure dependence of volume on composition
4 Fit observed volume/composition curve
4 Differentiate

 ð


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 = °


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= °


 Partial Molar Quantities - General

4 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
4 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, µ
 Partial Molar Free Energies
4 Chemical potential, µJ, is defined as the partial molar Gibbs energy @
constant P, T and other components
» µJ = (áG/ ánJ) p,T,n¶
» For a system of two components: G = nAµA + n B µB
4 G is a function of p,T and composition
» For an open system constant composition,
dG =Vdp - SdT + µA dnA + µB dn B
D


  
  

@ constant P and T this becomes, dG = µA dnA + µB dn B
* dG is the the non expansion work, dwmax
* FET implies changing composition can result in work, e.g. an
electrochemical cell
Chemical Potential
4 Gibbs energy, G, is related to the internal energy, U
U = G - pV + TS (G = U + pV - TS)
4 For an infinitesimal change in energy, dU
dU = -pdV - Vdp + TdS + SdT + dG
but
dG =Vdp - SdT + µA dnA + µB dn B
so
dU = -pdV - Vdp +TdS +SdT + Vdp - SdT + µA dnA + µB dn B
dU = -pdV + TdS + µA dnA + µB dn B
at constant V and S,
dU = µA dnA + µB dn B or µJ = (áU/ ánJ)S,V,n¶
µ and Other Thermodynamic Properties

4 Enthalpy, H (G = H - TS)
dH = dG + TdS + SdT
dH= (Vdp - SdT + µA dnA + µB dn B) - TdS SdT
dH = VdP - TdS + µA dnA + µB dn B



dH = µA dnA + µB dn B or µJ = (áH/ ánJ)p,T,n¶
4 Helmholz Energy, A (A = U-TS)
dA = dU - TdS - SdT
dA = (-pdV + TdS + µA dnA + µB dn B ) - TdS - SdT
dA = -pdV - SdT + µA dnA + µB dn B



dA = µA dnA + µB dn B or µJ = (áA/ ánJ)V,T,n¶
Gibbs-Duhem Equation

4 Recall, for a system of two components:

G = nAµA + n B µB
4 If compositions change infinitesimally
dG = µA dnA + µB dn B + nAdµA + n Bd µB
4 But at constant p & T, dG = µA dnA + µB dn B so
µA dnA + µB dn B = µA dnA + µB dn B + nAdµA + n Bd µB
or
nAdµA + n Bd µB = 0
4 For J components,
÷ nidµi = 0 (i=1,J) {6   

Significance of Gibbs-Duhem
4 Chemical potentials of multi-component systems
cannot change independently
» Two components, G-D says, nAdµA + n Bd µB = 0
means that d µB = (nA/ n B)dµA
4 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
You do this in Experiment 2
 Example Self Test 7.2
VA = 6.218 + 5.146b - 7.147b2
dVA = + 5.146 - 2*7.147b = + 5.146 - 14.294b db
dVA/db = + 5.146b - 14.294b
If *MB is in kg/mol
dVB = -nA/nB (dVA); b=nA/nB*MB or b *MB = nA/nB
'dVB = -'nA/nB (dVA ) = 'nA/nB dVA = 'b *MB dVA
'dVB = -' b* MB (5.146 - 14.294b) db =- MB(2.573b-4.765b2)
VB =VB* + MB (4.765b2 - 2.573b)
from data VB* = 18.079 cm3mol-1 and MB = 0.018 kg/mol
so
VB = 18.079 cm3mol-1 + 0.0858b2 - 0.0463b
 Thermodynamics of Mixing
4 For 2 Gases (A &B) in two containers, the Gibbs 6


energy, Gi   6 
Gi = nAµA + nBµB
» But µ = µ° + RTln(p/p°) so
Gi = nA(µA° + RTln(p/p°) )+ nB(µB° + RTln(p/p°))
» If p is redefined as the pressure relative to p°
Gi = nA(µA° + RTln(p) )+ nB(µB° + RTln(p) )
4 After mixing, p = pA + pB and
Gf = nA(µA° + RTln(pA) )+ nB(µB° + RTln(pB) )
4 So OGmix = Gf - Gi = nA (RTln(pA/p) )+ nB(RTln(pB /p)
4 Replacing nJ by xJn and pJ/p=xJ (from Dalton¶s Law)
O6 



 

 
This equation tells you change in Gibbs energy is
negative since mole fractions are always <1
 Example :Self-Test 7.3
4 2.0 mol H2(@2.0 atm) + 4 mol N2 (@3.0 atm) mixed at
const. V. What is OGmix?
Initial: pH2= 2 atm;VH2= 24.5 L; pN2= 3 atm;VN2= 32.8 L{Ideal Gas
Final: VN2= VH2= 57.3 L; therefore pN2= 1.717 atm; pH2= 0.855 atm;{Ideal Gas
OGmix = RT(nA ln (pA /p) + nBln(pB /p))
OGmix = (8.315 J/mol K)x(298 K)[2mol x ( ln(0.855/2) + 4 mol x (ln(1.717/3)]
OGmix = -9.7 J

What is OGmix under conditions of identical initial pressures?

xH2 = 0.333; xN2 = 0.667; n = 6 mol
OGmix = nRT(xA ln (xA ) + xBln(xB ))
OGmix = 6mol x( 8.315J/molK)x 298.15K{0.333ln0.333 +0.667ln0.667)
OGmix = -9.5 J
 Entropy and Enthalpy of Mixing
4 For OSmix, recall OG = OH - TOS


Therefore OSmix = -á OGmix / á T   6 
OSmix = - á[ nRT(xA ln (xA ) + xBln(xB ))] / á T
OSmix = - nR(xA ln (xA ) + xBln(xB )
» It follows that OSmix is always (+) since xJln(xJ ) is
always (-)
4 For OHmix
OH = OG + TOS ={nRT(xA ln (xA ) + xBln(xB )
+T{- nR(xA ln (xA ) + xBln(xB )
OH ={nRT(xA ln (xA ) + xBln(xB ) -
{nRT(xA ln (xA ) + xBln(xB )
OH = 0
» Thus driving force for mixing comes from
entropy change
 Chemical Potentials of Liquids
  ! 

4 At equilibrium chem. pot. of liquid = chem. pot. of vapor, µA(l) =

µA(g,p)
4 For pure liquid, µ*A(l) = µ°A + RT ln(p *A) [1]
4 For A in solution, µA(l) = µ°A + RT ln(p A) [2]
» Subtracing [1] from [2] :
µA(l) - µ*A(l) = RT ln(pA) + RT ln(p *A)
µA(l) - µ*A(l) = RT{ln(pA) - ln(p *A) = RT{ln(pA/p *A)
µA(l) = µ*A(l) + RT{ln(pA/p *A) [3]
4 Raoult¶s 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
4 Combining Raoult¶s law with [3] gives

  




 Ideal Solutions/Raoult¶s Law

4 Mixtures which obey Raoult¶s

Law throughout the
composition range are -



 



  
4 Phenomenology of Raoult¶s
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 Raoult¶s Law
4 Raoult¶s Law works well when components of a
mixture are structurally similar
» Wide deviations possible for dissimilar mixtures
4 Ideal-Dilute Solutions
» Henry¶s Law (William Henry)
For dilute solutions, v.p. of solute is proportional to
the mole fraction (Raoult¶s Law) but v.p. of the pure
substance is
 the constant of proportionality
Empirical constant, K, has dimensions of
pressure
pB = xBKB (Raoult¶s Law says pB = xBpB)
» Mixtures in which the solute obeys Henry¶s Law
and solvent obeys Raoult¶s 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 Henry¶s Law & Raoult¶s Law
4 Henry¶s law applies to the

 in ideal dilute


v solutions
v  
4 Raoult¶s law applies to


 in ideal dilute
     


v
solutions and 



 in ideal solutions
   
4 Real systems can (and do )
v 

deviate from both

  v v
 Applying Henry¶s Law
4 What is the mole fraction of dissolved hydrogen dissolved
in water if the over-pressure is 100 atmospheres?
Henry¶s 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
4 For Ideal Liquid Mixtures
» As for gases the ideal Gibbs energy of mixing is
OGmix = nRT(xA ln (xA ) + xBRTln(xB ))
» Similarly, the entropy of mixing is
OSmix = - nR(xA ln (xA ) + xBln(xB )
and OHmix is zero
4 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
4 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)
4 Thermodynamic properties of real solns expressed in terms of ideal solutions using



» Entropy: SE = OSmix - OSmixideal
» Enthalpy: HE = OSmix(because OHmixideal = 0)
Assume HE = nDRTxAxB where is const. D =w/RT
w is related to the energy of AB interactions relative to AA and BB interactions
D $ 0, mixing endothermic; D < 0, mixing exothermic solvent-solute interactions more favorable
than solvent-solvent or solute-solute interactions
4 Regular solution is one in which HE  0 but SE 0
» Random distribution of molecules but different energies of interactions
» GE = HE
» OGmix =



 


  + DRTxAxB (Ideal Portion + Excess)
 Activities of Regular Solutions
4 Recall the activity of a compound, a, is defined
a = šx where š = activity coefficient
4 For binary mixture, A and B, consideration of excess
Gibbs energy leads to the following relationships
(Margules¶ eqns)
ln šA = DxB2 and ln šB = DxA2 [1]
» As xB approaches 0, šA approaches 1
4 Since, aA = šAxA, from [1]
;
 ß


 °´

? ;
 4 If D = 0, this is Raoult¶s Law
 ? ;
V â
V ; V   V  4 If D < 0 (endothermic mixing),
â
V gives vapor pressures lower than
 ideal
4 If D $ 0 (exothermic mixing), gives
ß° ´
 â
V ;



 vapor pressures higher than ideal

 V
4 If xA<<1, becomes pA = xA eD pA*
» Henry¶s law with K = eD pA*
Colligative Properties of Dilute
Solutions
 Colligative Properties
4 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
4 Types of colligative properties
» Boiling Point Elevation
» Freezing Point Depression
» Osmotic pressure
 Colligative Properties - General
4 Assume
µ- So  » Solute not volatile

µ- Pure L u 
» Pure solute separates when
frozen
µ- Gas 4 When you add solute the chemical



  
µ- Sout on potential, µA becomes

µA = µA * + RT ln(xA) where
µA * = Chemical Potential of
Pure Substance
x A = mole fraction of the
solvent
T f (soent) Tb (soent)
4 Since ln(xA) in negative µA $ µA*
T f(pure) T b(pure)
T f (soent)< T (pure)
f Tb (soent)> T (pure)
b
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 Boiling Point Elevation
At equilibrium µ(gas) = µ(liquid) or µA(g) = µA *(l) + RTln(xA)
Rearranging,(µA(g) - µA *(l))/RT = ln(xA) = ln(1- xB)
But , (µA(g) - µA *(l)) = OG vaporization so
ln(1- xB) = OG vap. /RT
Substituting for OG vap. (OH vap. -T OS vap. ) {Ingnore T dependence of H & S)
ln(1- xB) = (OH vap. -T OS vap.)/RT = (OH vap. /RT) - OS vap./R
When xB = 0 (pure liquid A), ln(1) = (OH vap. /RTb) - OS vap./R = 0 or
OH vap. /RTb = OS vap./R where Tb= boiling point
Thus ln(1- xB) = (OH vap. /RT) - OH vap. /RTb = (OH vap. /R)(1/T- 1/Tb)
If 1$$ xB, (OH vap. /R)(1/T- 1/Tb)
- xB and if T
Tb and OT= T  Tb
Then (1/T- 1/Tb) = OT/Tb2 and (OH vap./R) OT/Tb2 = - xB so
OT= - xB Tb2 /(OH vap./R) or OT= - xB Kb where Kb = Tb2 /(OH vap./R)
Boiling Point Elevation
4 Kb is the ebullioscopic constant
» Depends on solvent not solute
» Largest values are for solvents with high boiling points
Water (Tb = 100°C) Kb = 0.51 K/mol kg -1
Acetic Acid (Tb = 118.1°C) Kb = 2.93 K/mol kg -1
Benzene (Tb = 80.2°C) Kb = 2.53 K/mol kg-1
Phenol (Tb = 182°C) Kb = 3.04 K/mol kg -1
 Freezing Point Depression
4 Derivation the same as for boiling point elevation except
» At equilibrium µ(solid) = µ(solid) or µA(g) = µA *(l) + RTln(xA)
» Instead of the heat of vaporization, we have heat of fusion
4 Thus, OT= - xB Kf where Kf = Tf2 /(OH fus./R)
4 Kf is the cryoscopic constant
Water (Tf = 0°C) Kf = 1.86 K/mol kg -1
Acetic Acid (Tf = 17°C) Kf = 3.9 K/mol kg -1
Benzene (Tf = 5.4°C) Kf = 5.12 K/mol kg-1
Phenol (Tf = 43°C) Kf = 7.27 K/mol kg -1
4 Again property depends on solvent not solute
 Temperature Dependence of Solubility
4 Not strictly speaking colligative property but can be estimated assuming
it is
4 Starting point the same - assume @ equilibrium µ is equal for two states
» First state is solid solute, µB(s)
» Second state is dissolved solute, µB(l)
µB(l) = µB*(l) + RT ln xB
» At equilibrium, µB(s) = µB(l)
µB(s) = µB*(l) + RT ln xB
» Same as expression for freezing point except that use xB instead of
xA
Temperature Dependence of Solubility

4 To calculate functional form of temperature dependence you solve for mole

fraction
» ln xB = [µB(s) - µB*(l)]/ RT = -OG fusion/RT = -[OH fus-T OS fus]/RT
» ln xB = -[OH fus-T OS fus]/RT = -[OH fus /RT] + [OS fus/R] {1
4 At the melting point of the solute, Tm, OG fusion/RTm = 0 because OG fusion = 0
» So [OH fus-Tm OS fus]/RTm = 0 or [OH fus /RTm] -[OS fus/R] = 0
» Substituting into {1, ln xB = -[OH fus /RT] + [OS fus/R]+ [OH fus /RTm] -[OS fus/R]
» This becomes ln xB = -[OH fus /RT] + [OH fus /RTm]
» Or ln xB = -[OH fus /R] [1/T - 1/Tm]
» Factoring Tm, ln xB = [OH fus /R Tm] [1 - (Tm /T)]
» Or xB = exp[OH fus /R Tm] [1 - (Tm /T)-1]
4 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
ln xB = -[OH fus /R] [1/T - 1/Tm]
or xB = exp[OH fus /R Tm] [1 - (Tm /T)-1]

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f s/RT*=ï 

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 Osmotic pressure
4 J. A. Nollet (1748) - ³wine 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
4 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
4 Osmotic pressure , r, is the pressure which must be applied to solution
to stop the influx of solvent
 Osmotic Pressure van¶t Hoff Equation

4 J. H. van¶t Hoff (1885) - In dilute solutions the osmotic pressure obeys the relationship,
rV=nBRT
» nB/V = [B] {molar concentration of B, so r=[B] RT
4 Derivation- at equilibrium µ solvent is the same on both sides of membrane: µA *(p) = µA
(x A,p +r) {1
» µA (x A,p +r) = µ*A (x A,p +r) + RTln(x A) {2
p +r
µ*A (x A,p +r) = µA *(p) + œp Vm dp {3 [Vm = molar volume of the pure
solvent]
p +r
Combining {1 and {2 : µA *(p) = µA *(p) + œp 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 +r p +r
œp V m dp = Vmœp dp = Vm r
So 0 = V m r + RT - x B or Vmr = RT x B
Now nA V m = V and, if solution dilute x B § - n B /nA so r=[B] RT
4 Non-ideality use a virial expansion
» r=[B] RT{1 + B[B] + ... where B I s the osmotic virial coef. (like pressure)
Application of Osmotic Pressure

4 Determine molar mass of

Sout on w th macromoecue macromolecules
» r=[B] RT{1 + B[B] + ... but [B] = c/M
where c is the concentration and M the molar
mass so
r = c/M RT{1 + Bc/M + ...
Water r
 w r  g h = c/M RT{1 + Bc/M + ...
h h/c = RT/(M g) {1 + Bc/M + ...
h/c = RT/(M g) + RTB/(M2 g) + ...
4 Plot of h/c vs. c has intercept of
RT/(M g) so
» Intercept= RT/(M g) or M=
RT/(intercept x g)
» Units (SI) are kg/mol typical Dalton
(Da) {1Da = 1g/ mol
Oembrane
Non-Ideality & Activities
Solvents

4 Recall for ideal solution µA =µA * + RTln(xA)

» µA* 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 µA =µA * + RTln(pA/ p*A)

‡ As xA-$ 1, aA -$ xA so define activity coefficient,š, such that

‡ aA = š A xA
‡ As xA-$ 1, šA -$ 1
4 Thus µA =µA * + RTln(xA) + RTln(šA) {substiuting for a A
 Non-Ideality & Activities
Solutes (Ideal & Non-Ideal)

4 For ideal dilute solutions Henry¶s Law ( pB = KBxB) applies

4 Chemical potential µB = µ B + RTln(pB /pB*)
» µB = µ B + RTln(KBxB /pB*) = µ B + RTln(KB/pB*) + RTln(xB )
KB and pB* are characteristics of the solute so you can combine them
with µ B
µB‚ = µ B + RTln(KBxB /pB*)
Thus µB = µ B‚ + RTln(xB )
4 Non-ideal solutes
» As with solvents introduce acitvity and activity coefficient
aB = pB/KB*; aB = š B xB
As xA-$ 0, aA -$ xA and šA -$ 1
 Activities in Molalities
4 For dilute solutions x B § n B /nA , and x B = X b/b°
» kappa, X , is a dimensionless constant
4 For ideal-dilute solution, µB = µ B‚ + RTln(xB ) so µB = µ B‚ + RTln(X b/b°) =
µ B‚+ RTln(X) + RTln( b/b°)
4 Dropping b° and combing 1st 2 terms, µB = µ Bø+ RTln( b)
» µ Bø = µ B‚+ RTln(X)
» µB has the standard value (µBø ) when b=b°
» As b -$0, µB -$infinity so dilution stabilizes system
Difficult to remove last traces of solute from a soln
4 Deviations from ideality can be accounted for by defining an activity aB and
activity,š B,
» aB = š B bB/b° where š B -$1, bB -$ 0
4 The chemical potential then becomes µ = µø + RTln( a)
4 Table 7.3 in book summarizes the relationships