Freezing-point depression

Saltwater freezing point

Freezing-point depression is the decrease of the freezing point of a solvent on the addition of a

non-volatile solute. Examples include salt in water, alcohol in water, or the mixing of two solids
such as impurities into a finely powdered drug. In all cases, the substance added/present in
smaller amounts is considered the solute, while the original substance present in larger quantity
is thought of as the solvent. The resulting liquid solution or solid-solid mixture has a lower
freezing point than the pure solvent or solid because the chemical potential of the solvent in the
mixture is lower than that of the pure solvent, the difference between the two being proportional
to the natural logarithm of the mole fraction. In a similar manner, the chemical potential of the
vapor above the solution is lower than that above a pure solvent, which results in boiling-point
elevation. Freezing-point depression is what causes sea water, (a mixture of salt and other
compounds in water), to remain liquid at temperatures below 0 °C (32 °F), the freezing point of
pure water.

Explanation

The freezing point is the temperature at which the liquid solvent and solid solvent are at
equilibrium, so that their vapour pressures are equal. When a non-volatile solute is added to a
volatile liquid solvent, the solution vapour pressure will be lower than that of the pure solvent.
As a result, the solid will reach equilibrium with the solution at a lower temperature than with the
pure solvent.[1] This explanation in terms of vapor pressure is equivalent to the argument based
on chemical potential, since the chemical potential of a vapor is logarithmically related to
pressure. All of the colligative properties result from a lowering of the chemical potential of the
solvent in the presence of a solute. This lowering is an entropy effect. The greater randomness of
the solution (as compared to the pure solvent) acts in opposition to freezing, so that a lower
temperature must be reached, over a broader range, before equilibrium between the liquid
solution and solid solution phases is achieved. Melting point determinations are commonly
exploited in organic chemistry to aid in identifying substances and to ascertain their purity.

Uses
Ice
on a road

The phenomenon of freezing-point depression has many practical uses. The radiator fluid in an
automobile is a mixture of water and ethylene glycol. The freezing-point depression prevents
radiators from freezing in winter. Road salting takes advantage of this effect to lower the freezing
point of the ice it is placed on. Lowering the freezing point allows the street ice to melt at lower
temperatures, preventing the accumulation of dangerous, slippery ice. Commonly used sodium
chloride can depress the freezing point of water to about −21 °C (−6 °F). If the road surface
temperature is lower, NaCl becomes ineffective and other salts are used, such as calcium
chloride, magnesium chloride or a mixture of many. These salts are somewhat aggressive to
metals, especially iron, so in airports safer media such as sodium HYPERLINK
"https://en.wikipedia.org/wiki/Sodium_formate"formate, potassium HYPERLINK
"https://en.wikipedia.org/wiki/Potassium_formate"formate, sodium acetate, potassium acetate are
used instead.

Freezing-point depression is used by some organisms that live in extreme cold. Such creatures
have evolved means through which they can produce a high concentration of various compounds
such as sorbitol and glycerol. This elevated concentration of solute decreases the freezing point
of the water inside them, preventing the organism from freezing solid even as the water around
them freezes, or as the air around them becomes very cold. Examples of organisms that produce
antifreeze compounds include some species of arctic-living fish such as the rainbow smelt, which
produces glycerol and other molecules to survive in frozen-over estuaries during the winter
months.[2] In other animals, such as the spring peeper frog (Pseudacris crucifer), the molality is
increased temporarily as a reaction to cold temperatures. In the case of the peeper frog, freezing
temperatures trigger a large-scale breakdown of glycogen in the frog's liver and subsequent
release of massive amounts of glucose into the blood.[3]

With the formula below, freezing-point depression can be used to measure the degree
of dissociation or the molar mass of the solute. This kind of measurement is
called cryoscopy (Greek cryo = cold, scopos = observe; "observe the cold"[4]) and relies on exact
measurement of the freezing point. The degree of dissociation is measured by determining
the van 't HYPERLINK "https://en.wikipedia.org/wiki/Van_%27t_Hoff_factor" Hoff factor i by
first determining mB and then comparing it to msolute. In this case, the molar mass of the solute
must be known. The molar mass of a solute is determined by comparing mB with the amount of
solute dissolved. In this case, i must be known, and the procedure is primarily useful for organic
compounds using a nonpolar solvent. Cryoscopy is no longer as common a measurement method
as it once was, but it was included in textbooks at the turn of the 20th century. As an example, it
was still taught as a useful analytic procedure in Cohen's Practical Organic Chemistry of 1910,
[5]
 in which the molar mass of naphthalene is determined using a Beckmann freezing apparatus.
Freezing-point depression can also be used as a purity analysis tool when analyzed
by differential scanning HYPERLINK
"https://en.wikipedia.org/wiki/Differential_scanning_calorimetry"calorimetry. The results
obtained are in mol%, but the method has its place, where other methods of analysis fail.

This is also the same principle acting in the melting-point depression observed when the melting
point of an impure solid mixture is measured with a melting-point apparatus since melting and
freezing points both refer to the liquid-solid phase transition (albeit in different directions).

In principle, the boiling-point elevation and the freezing-point depression could be used
interchangeably for this purpose. However, the cryoscopic constant is larger than
the ebullioscopic constant, and the freezing point is often easier to measure with precision, which
means measurements using the freezing-point depression are more precise.

Also, this phenomenon is applicable in preparing a freezing mixture for use in an ice-cream
machine. For this purpose, NaCl or another salt is used to lower the melting point of ice.

Last but not the least, FPD measurements are used in the dairy industry to ensure that milk has
not had extra water added. Milk with a FPD of over 0.509 °C is considered to be unadulterated.[6]

Of a solvent and a nonvolatile solute

Consider the problem in which the solvent freezes to a very nearly pure crystal, regardless of the
presence of the nonvolatile solute. This typically occurs simply because the solute molecules do
not fit well in the crystal, i.e. substituting a solute for a solvent molecule in the crystal has
high enthalpy. In this case, for low solute concentrations, the freezing point depression depends
solely on the concentration of solute particles, not on their individual properties. The freezing
point depression thus is called a colligative property.

The explanation for the freezing point depression is then simply that as solvent molecules leave
the liquid and join the solid, they leave behind a smaller volume of liquid in which the solute
particles can roam. The resulting reduced entropy of the solute particles thus is independent of
their properties. This approximation ceases to hold when the concentration becomes large
enough for solute-solute interactions to become important. In that case, the freezing point
depression depends on particular properties of the solute other than its concentration.

Calculation for dilute solution

If the solution is treated as an ideal solution, the extent of freezing-point depression depends only
on the solute concentration that can be estimated by a simple linear relationship with the
cryoscopic constant ("Blagden's Law"):

ΔTF = KF · b · i,

Where:

• ΔTF, the freezing-point depression, is defined as TF (pure solvent) − TF (solution).

• KF, the cryoscopic constant, which is dependent on the properties of the solvent, not the
solute. (Note: When conducting experiments, a higher KF value makes it easier to
observe larger drops in the freezing point. For water, KF = 1.853 K·kg/mol.[8])

• b is the molality (moles solute per kilogram of solvent)

• i is the van 't Hoff factor (number of ion particles per formula unit of solute, e.g. i = 2 for
NaCl, 3 for BaCl2).
Values of cryoscopic constants[edit]
Values of the cryoscopic constant Kf for selected solvents:[9]

Compound Freezing point (°C) Kf in K⋅kg/mol

Acetic acid 16.6 3.90

Benzene 5.5 5.12

Camphor 179.8 39.7

Carbon disulfide −112 3.8

Carbon tetrachloride −23 30

Chloroform −63.5 4.68

Cyclohexane 6.4 20.2

Ethanol −114.6 1.99

 Ethyl ether −116.2 1.79

Naphthalene 80.2 6.9

Phenol 41 7.27

Water 0 1.86

More accurate equation for concentrated solution[edit]

The simple relation above doesn't consider the nature of the solute, so it is only effective in a
diluted solution. For a more accurate calculation at a higher concentration, for ionic solutes,
Ge and Wang (2010)[10][11] proposed a new equation:

In the above equation, TF is the normal freezing point of the pure solvent (273 K for
water, for example); aliq is the activity of the solvent in the solution (water activity for
aqueous solution); ΔHfusT  is the enthalpy change of fusion of the pure solvent at TF, which
F

is 333.6 J/g for water at 273 K; ΔCfusp is the difference between the heat capacities of the
liquid and solid phases at TF, which is 2.11 J/(g·K) for water.

The solvent activity can be calculated from the Pitzer model or modified TCPC model,
which typically requires 3 adjustable parameters. For the TCPC model, these parameters
are available for many single salts.

Boiling-point elevation
Boiling-point elevation describes the phenomenon that the boiling point of a liquid (a solvent) will be higher
when another compound is added, meaning that a solution has a higher boiling point than a pure solvent. This
happens whenever a non-volatile solute, such as a salt, is added to a pure solvent, such as water. The boiling
point can be measured accurately using an ebullioscope.

Explanation

The change in chemical potential of a solvent when a solute is added explains why boiling point elevation takes place.

The boiling point elevation is a colligative property, which means that it is dependent on the presence of
dissolved particles and their number, but not their identity. It is an effect of the dilution of the solvent in the
presence of a solute. It is a phenomenon that happens for all solutes in all solutions, even in ideal solutions, and
does not depend on any specific solute–solvent interactions. The boiling point elevation happens both when the
solute is an electrolyte, such as various salts, and a nonelectrolyte. In thermodynamic terms, the origin of the
boiling point elevation is entropic and can be explained in terms of the vapor pressure or chemical potential of
the solvent. In both cases, the explanation depends on the fact that many solutes are only present in the liquid
phase and do not enter into the gas phase (except at extremely high temperatures).

Put in vapor pressure terms, a liquid boils at the temperature when its vapor pressure equals the surrounding
pressure. For the solvent, the presence of the solute decreases its vapor pressure by dilution. A nonvolatile
solute has a vapor pressure of zero, so the vapor pressure of the solution is less than the vapor pressure of the
solvent. Thus, a higher temperature is needed for the vapor pressure to reach the surrounding pressure, and the
boiling point is elevated.

Put in chemical potential terms, at the boiling point, the liquid phase and the gas (or vapor) phase have the
same chemical potential (or vapor pressure) meaning that they are energetically equivalent. The chemical
potential is dependent on the temperature, and at other temperatures either the liquid or the gas phase has a
lower chemical potential and is more energetically favorable than the other phase. This means that when a
nonvolatile solute is added, the chemical potential of the solvent in the liquid phase is decreased by dilution,
but the chemical potential of the solvent in the gas phase is not affected. This means in turn that the
equilibrium between the liquid and gas phase is established at another temperature for a solution than a pure
liquid, i.e., the boiling point is elevated.[1]

The phenomenon of freezing-point depression is analogous to boiling point elevation. However, the magnitude
of the freezing point depression is larger than the boiling point elevation for the same solvent and the same
concentration of a solute. Because of these two phenomena, the liquid range of a solvent is increased in the
presence of a solute.

The equation for calculations at dilute concentration [edit]

The extent of boiling-point elevation can be calculated by applying Clausius–Clapeyron relation and Raoult's
law together with the assumption of the non-volatility of the solute. The result is that in dilute ideal solutions,
the extent of boiling-point elevation is directly proportional to the molal concentration (amount of substance
per mass) of the solution according to the equation:[1]

ΔTb = Kb · bB

where the boiling point elevation, is defined as Tb (solution) - Tb (pure solvent).

• Kb, the ebullioscopic constant, which is dependent on the properties of the solvent. It can be calculated
 as Kb = RTb2M/ΔHv, where R is the gas constant, and Tb is the boiling temperature of the pure solvent
[in K], M is the molar mass of the solvent, and ΔHv is the heat of vaporization per mole of the solvent.

• bB is the molality of the solution, calculated by taking dissociation into account since the boiling point
elevation is a colligative property, dependent on the number of particles in solution. This is most
easily done by using the van 't HYPERLINK "https://en.wikipedia.org/wiki/Van_%27t_Hoff_factor"
Hoff factor i as bB = bsolute · i. The factor i accounts for the number of individual particles (typically
ions) formed by a compound in solution. Examples:

• i = 1 for sugar in water

• i = 1.9 for sodium chloride in water, due to the near full dissociation of NaCl into Na+ and
Cl− (often simplified as 2)

• i = 2.3 for calcium chloride in water, due to nearly full dissociation of CaCl2 into Ca2+ and
2Cl− (often simplified as 3)

Non integer i factors result from ion pairs in solution, which lower the effective number of particles in the
solution.

Equation after including the van 't Hoff factor

ΔTb = Kb · bsolute · i

At high concentrations, the above formula is less precise due to nonideality of the solution. If the
solute is also volatile, one of the key assumptions used in deriving the formula is not true, since it
derived for solutions of non-volatile solutes in a volatile solvent. In the case of volatile solutes it is
more relevant to talk of a mixture of volatile compounds and the effect of the solute on the boiling
point must be determined from the phase diagram of the mixture. In such cases, the mixture can
sometimes have a boiling point that is lower than either of the pure components; a mixture with a
minimum boiling point is a type of azeotrope.

Ebullioscopic constants
Values of the ebullioscopic constants Kb for selected solvents:[2]

Boiling point in Ebullioscopic constant Kb in units of [(°C·kg)/mol] or

Compound
°C [°C/molal]

Acetic acid 118.1 3.07

Benzene 80.1 2.53

 Carbon disulfide 46.2 2.37

Carbon
76.8 4.95
tetrachloride

Naphthalene 217.9 5.8

Phenol 181.75 3.04

Water 100 0.512

Uses
Together with the formula above, the boiling-point elevation can in principle be used to measure the
degree of dissociation or the molar mass of the solute. This kind of measurement is
called ebullioscopy (Greek "boiling-viewing"). However, since superheating is difficult to avoid,
precise ΔTb measurements are difficult to carry out,[1] which was partly overcome by the invention of
the Beckmann thermometer. Furthermore, the cryoscopic constant that determines freezing-point
depression is larger than the ebullioscopic constant, and since the freezing point is often easier to
measure with precision, it is more common to use cryoscopy.

Among many urban legends related to the effect of ebullioscopic increase, one of them leads to
adding salt when cooking pasta only after water has started boiling. The misconception is that since
the water boils at a higher temperature, food will cook faster. However, at the approximate
concentration of salt in water for cooking (10 g of salt per 1 kg of water, or 1 teaspoon per quart), the
ebullioscopic increase is approximately 0.17 °C (0.31 °F), which will arguably make no practical
difference for cooking, although salt may add to flavors.