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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #23

page 1

Colligative Properties

These are properties of solutions in the dilute limit, where there is a

solvent A and a solute B where nA >> nB.

mix These properties are a direct result of A (l, T, p) < A pure

(l, T, p)

Use two measures of concentration:

a. Mole Fraction: xB = nB/(nA+nB) ~ nB/nA b. Molalility: mB = (moles solute)/(kg solvent) = nB/(nAMA) Where MA is the mass in kg of one mole of solvent. There are FOUR Colligative Properties: 1. V apor pressure lowering:
* * pA = pA pA = xB pA

2. Boiling point elevation:

Tb = Tb Tb* = Kb mB

Kb = 3. Freezing point depression:

MA R Tb* Hvap

( )

Tf = Tf Tf* = Kf mB

Kf = 4. Osmotic pressure:
~ = RTc

MA R Tf* Hf

( )

~ = nB is concentration of solute where c V

5.60 Spring 2008

Lecture #23

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Lets go through these one at a time: 1. Vapor pressure lowering: This is just Raoults Law.
* * pA = xA pA = (1 xB )pA

So

* * pA = pA pA = xB pA (<0)

2.

Boiling point elevation:

A (l, T, p) = A (g, T, p)

Lets derive this. Start with So, And

* A (l, T, p) + RT ln xA = A (g, T, p)

ln xA =

Gvap 1 * [ A (g, T, p) A (l, T, p)] = RT RT

But lnxA = ln(1-xB) ~ -xB = -nB/(nA+nB) ~ -nB/nA = -(MnB)/(MnA) Where M is the total mass of A, So, lnxA ~ mBMA, where MA is the molar mass of A. Putting it all together then, But we need T in there!
Gvap T Hvap 1 mB = = 2 T M RT T p MAR A p

mB =

Gvap MA RT

which gives us T =

MA RT 2 Hvap

mB

5.60 Spring 2008

Lecture #23

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If mB = mB 0 (mixed pure) and mB is very small Then

T = Tb Tb* = MA R(Tb* ) 2 Hvap mB = Kb mB

3.

Freezing point depression: Gvap with Gf Hvap with Hf Tb with Tf Kb with Kf

Same arguments as above, replacing

4.

Osmotic Pressure: The pressures at points:

h
A+B

pext

: :

p = pext + g p + = pext + g + h g

At equilibrium: Using Raoults Law: At constant T:

* A (l, p + , T) = A (l, p, T) * * RT ln xA + A (l, p + , T) A (l, p, T) = 0 * = VA* dp dG = Vdp, or d A

5.60 Spring 2008

Lecture #23
p +

page 4

Integrating

* A (l, p

+ , T)

* A (l, p, T)

VA dp = VA
p

(this assumed an incompressible liquid, where volume does not depend on p) So then RT ln xA + VA* = 0 Again using lnxA ~ -nB/nA Then RT(-nB/nA) + (VA/nA) = 0 But VA ~ VA + VB = V So finally, (VB<<VA) V = RTnB

This is the Vant Hoff Equation. It looks like the ideal gas law!

~ = n /V in the Vant Hoff Eq., then we get the osmotic

If we replace c B pressure relation:
~ = RTc