material impurities

Heating coil 7.8 | Colligative Properties 209

(b)

(a)

James P. Blair/National Geographic Stock

Heating coil
Purified Collected
material impurities

(a) (b) (c)

Figure 7.26 In zone refining of silicon, a heating coil melts a small part of the boule at a time. As the liquid
slowly solidifies, impurities remain concentrated in the liquid phase. As the molten zone passes along the
Purified
boule, Collectedare collected at one end, which can then be removed from the pure material.
eventually the impurities
material impurities

7.8 Colligative Properties

Consider the solvent of a solution. It is typically defined as the component with the
majority mole fraction, although with concentrated aqueous solutions this defini-
(b)
tion is often relaxed. Compare the properties of a solution with a nonvolatile solute
with the same properties of the pure solvent. In certain cases, the physical properties
are different. These properties differ because of the presence of solute molecules. The
properties are independent of the identity of the solute molecules, and the change in
the property is related only to the number of solute molecules. These properties are
(c)
called colligative properties, where the word colligative comes from the Latin words
meaning “to bind together,” which is what the particles of solute and solvent are
doing, in a sense. The four common colligative properties are vapor pressure depres-
sion, boiling point elevation, freezing point depression, and osmotic pressure.
We have already addressed vapor pressure depression, in the form of Raoult’s
law. The vapor pressure of a pure liquid is lowered when a solute is added, and the
vapor pressure is proportional to the mole fraction of the solvent:
(c) psolv 5 xsolv p*solv
where psolv is the true pressure of the solvent, p*solv is the vapor pressure of the pure
solvent, and xsolv is the mole fraction of the solvent in the solution. Because mole
fractions are always 1 or less, the vapor pressure of a solvent in a solution is always
less than the vapor pressure of the pure liquid. Notice, too, that Raoult’s law doesn’t
care what the solute is; it only depends on the mole fraction of the solvent. This is
one of the characteristics of a colligative property. It’s not what, but how much.
From a molecular level, it is easy to rationalize why nonvolatile solutes lower the
vapor pressure of the solvent. Figure 7.27 shows a molecular representation of a pure
solvent and a solution with a nonvolatile solute. The particles of solute literally block
the solvent molecules from escaping into the vapor phase, thus lowering the equilib-
rium vapor pressure of the solution with respect to the pure liquid.

Pure solvent Solution

Figure 7.27 Rate of evaporation from solution. When a solution forms, the presence of the solute
­ articles reduces the rate of evaporation of the solvent, thus decreasing the equilibrium vapor pressure.
p
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210 Chapter 7 | Equilibria in Multiple-Component Systems

Before considering the next colligative properties, we recall the concentration

unit molality. The molality of a solution is similar to molarity except that it is
defined in terms of the number of kilograms of solvent, not liters of solution:
number of moles of solute
molality ; (7.40)
number of kilograms of solvent
Molality, abbreviated molal or m, is useful for colligative properties because it is a
more direct ratio of molecules of solute to molecules of solvent. The unit molarity
automatically includes the concept of partial molar volumes because it is defined in
terms of liters of solution, not liters of solvent. It is also dependent on the amounts
of solvent and solute (in mole and kilogram units), but independent of volume
or temperature. Thus, as T changes, the concentration in molality units remains
constant while the concentration in molarity units varies due to expansion or
contraction of the solution’s volume.
The next colligative property is boiling point elevation. A pure liquid has a well-
defined boiling point at a particular pressure. If a nonvolatile solute were added,
then to some extent those solute molecules would impede the ability of solvent
molecules to escape from the liquid phase, so more energy is required to make the
liquid boil, and the boiling point increases.
Similarly, nonvolatile solutes will make it harder for solvent molecules to crystal-
lize at their normal melting points because solidification will be impeded. Therefore,
a lower temperature will be required to freeze the pure solvent. This defines the idea
of freezing point depression. A pure liquid will have its freezing point lowered when a
solute is dissolved in it. (This idea is a common one for anyone who has tried to syn-
thesize a compound in a lab. An impure compound will melt at a lower temperature
because of the freezing point depression of the “solvent.”)
Because the liquid-gas and liquid-solid transitions are equilibria, we can apply
some of the mathematics of equilibrium processes to the changes in phase transi-
tion temperatures. In both cases the argument is the same, but here we will concen-
trate on the liquid-solid phase equilibrium and then apply the final arguments to
the liquid-gas phase change.
In some respects, the freezing point depression can be considered in terms of
solubility limits, which we discussed in the previous section. This time, instead of
the component of interest being the solute, the component of interest is the solvent.
However, the same arguments and equations apply. By analogy, we can adapt equa-
tion 7.39 and say that
DfusH 1 1
ln xsolvent 5 2 a 2 b (7.41)
R T TMP
where DfusH and TMP refer to the enthalpy of fusion and melting point of the
solvent. If we are considering dilute solutions, then xsolvent is very close to 1. Because
xsolvent 5 1 2 xsolute, we can substitute to get
DfusH 1 1
ln (1 2 xsolute) 5 2 a 2 b (7.42)
R T TMP
Using a one-term Taylor-series expansion of ln (1 2 x) < 2 x,* we substitute for
the logarithm on the left side of the equation and get
DfusH 1 1
xsolute < a 2 b (7.43)
R T TMP

*The multiterm expansion is ln(1 2 x) 5 2x 2 12x2 2 13x3 2 14x4 2 # # # .

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 7.8 | Colligative Properties 211

where the minus signs have canceled. This equation is rewritten by algebraically
rearranging the temperature terms:
DfusH TMP 2 T
xsolute < (7.44)
R T # TMP
We make one last approximation. because we are working with dilute solutions,
the temperature of the equilibrium is not much different from the normal melting
point temperature TMP. (Recall that the freezing point and the melting point are the
same temperature and that the phrases “freezing point” and “melting point” can
be used interchangeably.) Therefore, we substitute TMP for T in the denominator
of equation 7.44, and define DTf as TMP 2 T: the change in temperature of the
equilibrium melting or freezing process. Equation 7.44 becomes
DfusH
xsolute < DTf (7.45)
RT 2MP
The relationship between molality and mole fraction is simple. If Msolvent is the
molecular weight of the solvent, then the molality of the solution is
1000 # xsolute
msolute 5 (7.46)
xsolvent # Msolvent
The 1000 in the numerator of equation 7.46 represents a conversion from grams to
kilograms, so there is an implicit g/kg unit on it. Remember that the mole fraction
of the solvent is close to 1, so we further approximate by substituting 1 for xsolvent.
We then rearrange equation 7.46 in terms of xsolute, substitute into equation 7.45,
and then rearrange the equation to get an expression for DTf , the amount that the
freezing point is depressed. We get
Msolvent # RTMP
2
DTf < a bmsolute (7.47)
1000 # DfusH
All of the terms relating to properties of the solvent have been grouped inside
parentheses, and the only term relating to the solute is its molal concentration.
Notice that all of the terms inside the parentheses are a constant for any particu-
lar solvent: its molecular weight Msolvent, its melting point TMP, and its enthalpy of
fusion DfusH. (1000 and R are also constants.) Therefore, this collection of constants rep-
resents a constant value for any solvent. Equation 7.47 is more commonly written as
DTf < Kf # msolute (7.48)
where Kf is called the freezing point depression constant for the solvent. It is also
called the cryoscopic constant for the solvent.

Example 7.14

Calculate the cryoscopic constant for cyclohexane, C6H12, given that its enthalpy of
fusion is 2630 J/mol and its melting point is 6.6°C. What are the units for the constant?

Solution
The molecular weight of cyclohexane is 84.16 g/mol. The melting point, which
must be expressed in absolute temperature, is 6.6 1 273.15 5 279.8 K. Comparing
equations 7.47 and 7.48, we see that the expression for Kf is
2
Msolvent RTMP
Kf 5
1000 DfusH

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