Thermochemistry / Calorimetry LEC 02

02.11 Freezing point depression

What you can learn about

 Raoults law
 Cryoscopy
 Chemical potential
 Gibbs-Helmholtz equation
 Vant Hoff factor

Principle and tasks

The freezing point of a solution is
lower than that of the pure solvent.
The depression of the freezing point
can be determined experimentally
using a suitable apparatus (cryos-
copy). If the cryoscopy constants of
the solvent are known, the molecular
mass of the dissolved substances can
be determined.

What you need:

Apparatus for freezing point depression 36821.00 1
Gasket for GL 25, 12 mm hole 41243.03 1
Temperature meter digital, 4-2 13617.93 1
Temperature probe, Pt100 11759.01 2
Protective sleeves for temperature probe 11762.05 1
Magnetic heating stirrer 35750.93 1
Magnetic stirrer bar, l = 30 mm 46299.02 1
Support rod, stainless steel, l = 500 mm, M10 thread 02022.20 1
Right angle clamp 37697.00 2
Universal clamp 37715.00 2
Glass beaker, 1000 ml, short 36017.00 1
Volumetric pipette, 50 ml 36581.00 1
Pipettor 36592.00 1
Precision balance CPA 623S (620 g/0.001 g),
set with software 49224.88 1
Weighing dishes, 805014 mm 45019.25 1
Stopwatch, digital, 1/100 s 03071.01 1
Pellet press for calorimeter 04403.04 1
Mortar with pestle, 70 ml, porcelain 32603.00 2 Cooling curve of a water/table salt mixture.
Microspoon 33393.00 1
Spoon 33398.00 1
Funnel, plastic, do = 50 mm 36890.00 1
Pasteur pipettes 36590.00 1
Rubber bulbs 39275.03 1
Glass rod, l = 300 mm, d = 8 mm 40485.06 1
Wash bottle, 500 ml 33931.00 1
Sodium chloride, 500 g 30155.50 1
Hydroquinone, 250 g 30089.25 1
Raw alcohol for burning, 1000 ml 31150.70 1
Water, distilled, 5 l 31246.81 1

Freezing point depression P3021101

32 Laboratory Experiments Chemistry PHYWE Systeme GmbH & Co. KG D - 37070 Gttingen
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Freezing point depression
02.11

Related concepts Magnetic stirrer bar, l = 30 mm 46299.02 1

Raoults law, cryoscopic constant, chemical potential, Gibbs- Support rod, l = 500 mm, M10 thread 02022.20 1
Helmholtz equation, concentration ratio, degree of dissociation, Right angle clamp 37697.00 2
Vant Hoff factor. Universal clamp 37715.00 2
Glass beaker, 1000 ml, short 36017.00 1
Principle Volumetric pipette, 50 ml 36581.00 1
The freezing point of a solution is lower than that of the pure sol- Pipettor 36592.00 1
vent. The depression of the freezing point can be determined Set of precision balance Sartorius CPA623S
experimentally using a suitable apparatus (cryoscopy). If the and measure software 49224.88 1
cryoscopic constants of a solvent are known, the molecular Weighing dishes, 80 x 50 x 14 mm 45019.25 1
mass of the substance dissolved in it can be determined. Stopwatch, digital, 1/100 s 03071.01 1
Pellet press for calorimeter 04403.04 1
Tasks Mortar with pestle, 70 ml, porcelain 32603.00 2
1. Determine the size of freezing point depression after dissolv- Microspoon 33393.00 1
ing a strong electrolyte (NaCl) in water. By comparing the Spoon 33398.00 1
experimental value with the theoretical one predicted for this Funnel, plastic, do = 50 mm 36890.00 1
concentration, determine the number of ions into which the Pasteur pipettes 36590.00 1
electrolyte dissociates. Rubber bulbs 39275.03 1
2. Determine the molar mass of a non-electrolyte (hydro- Glass rod, l = 300 mm, d = 8 mm 40485.06 1
quinone) from the value of freezing point depression. Wash bottle, 500 ml 33931.00 1
Sodium chloride, 500 g 30155.50 1
Hydroquinone, 250 g 30089.25 1
Equipment Raw alcohol for burning, 1000 ml 31150.70 1
Apparatus for freezing point depression 36821.00 1 Water, distilled, 5 l 31246.81 1
Gasket for GL25, 12 mm hole 41243.03 1 Ice (approximately 3 kg)
Temperature meter digital, 4-2 13617.93 1 Vice
Temperature probe, Pt100 11759.01 2
Protective sleeves for temperature probe 11762.05 1 Set-up and procedure
Magnetic heating stirrer 35750.93 1 Set up the experiment as shown in Fig. 1.

Fig. 1. Experimental set-up.

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen P3021101 1
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Freezing point depression
02.11

The apparatus for depression of the freezing point consists of
two cylindrical glass vessels, arranged concentrically and con-
nected with a GL 45 screw assembly. The outer vessel resem-
bles a boiling tube and acts as a jacket around the inner vessel
(freezing vessel). Fill the jacket with approximately 35 to 40 ml of
ethanol (raw alcohol can also be used). This intermediating
medium ensures uniform heat conductance between the inner
and outer vessels. The inner vessel is intended for the solution
or the solvent whose freezing point is to be determined. On the
upper end of the inner vessel there is a screw cap for a ther-
mometer or a temperature probe and a tubular glass sleeve with
a screw cap (GL 18) for introducing the substance which is to be
dissolved. The bottom of the inner vessel is flat so that a small
stirrer bar (l = 15 mm) can rotate without hindrance.
The substances to be tested must be pressed into pellets so that
they can be inserted in the inner vessel without powder sticking
to the walls of the vessel. Weigh out five portions of each sub-
stance (NaCl, hydroquinone), each of approximately 600 mg. It
is advisable to first pulverise the substances with a mortar and
pestle. Use the pellet press as follows: Place it in a vertical posi-
tion and put the small steel rod in the cylinder to close the bot-
tom end of the borehole. Fill one portion of the substance into
the hole using a funnel. Next insert the large rod from above and
compress the substance a little. Fit the assembled press in a
vice and apply pressure on it, so that a solid pellet is formed from
the substance. Press the pellet out of the borehole with the
longer rod. Weigh the pellets to an accuracy of 1 mg.
Theory and evaluation
The vapour pressure of a liquid substance is lowered when the
liquid is cooled. At the freezing point, the vapour pressures of the
liquid and solid phases are the same. As the vapour pressure of
a solution is always lower than that of the pure solvent, howev-
er, the freezing point will be depressed. The two phenomena,
depression of the freezing point and elevation of the boiling
point, extend the range of the liquid phase at each end, provid-
ed that only the pure solvent crystallizes out or vaporizes.
The chemical potential mlA of substance A in the mixed phase at
a high concentration of A is
mlA  mAl  RT lnxA (1)
The chemical potential of the pure solid phase msA in equilibrium
with the fluid phase corresponds to the chemical standard
potential mAs of A, i.e. msA = mAs . When the two phases are in
equilibrium ( msA  mlA ) the following expression is obtained:
mAl  mAs  RT lnxA (2)
Since the chemical potential of pure substances is identical with
the molar free enthalpy GF, equation (2) becomes
G Al
G As  RT lnxA (3)
From the Gibbs-Helmholtz equation

The measurement consists of two steps. The cooling curve of d1G>T 2 H

the pure water is first to be plotted, then that of the solution 
; p  const. (4)
dT T2
resulting on addition of a pellet.
Pipette 50 ml of distilled water into the inner vessel and add the and through differentiation of equation (3), the following is
magnetic stirrer bar. Insert the protective sleeve for the temper- obtained:
ature sensor into the screw connection using a 12 mm bore gas-
ket instead of the original one. Drop a few drops of raw alcohol
onto the protective sleeve to improve heat transfer. Insert the H As
H Al FH d lnxA
2
 2
 (5)
temperature probe and connect it to the digital temperature RT RT dT
meter. When the apparatus is fully assembled, fix the device to
the support rod and position it as low as possible in the 1000 ml
beaker. Set the magnetic stirrer to a medium stirring speed. Fill
the beaker with an ice / salt freezing mixture and immerse the
second temperature probe. Adjust the temperature of the freez- Fig. 2: Cooling curve of water/table salt (NaCl) mixture
ing mixture to around 10C by adding water. When the temper-
ature in the inner vessel has reached approximately 1C, set the
digital temperature meter to measure the change in temperature
over time T (accuracy 0.01 K) and start recording the relative
temperatures every minute.

In the initial phase, a metastable condition develops which is

characterised by a temperature minimum. As soon as crystalli-
sation starts, the temperature begins to rise again until it reach-
es a maximum level (freezing point). From this critical point on a
cooling curve can be observed.
After the cooling curve of 50 ml of pure water has been record-
ed, lift the apparatus out of the freezing mixture and wait until the
water in the inner vessel has completely liquefied (this process
can be speeded up by hand warming). Then introduce a pellet of
the substance under investigation into the inner vessel and let it
dissolve completely. Lower the apparatus again into the freezing
mixture and start a new measurement (from the same initial tem-
perature as before). The resulting plot allows the freezing point
of the mixture to be determined.
Thoroughly clean and dry the inner vessel before each further
measurement is performed.

2 P3021101 PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen
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Freezing point depression
02.11

The fusion enthalpy FH can be considered to be constant for The constant Kc is known as the molar freezing point depression
small temperature changes. Integration of (5) between the limit- or the cryoscopic constant.
ing values for the pure solvent (xA = 1, T = T0) and for the solu- When determining the molar mass of a dissolved substance, the
tion (xA, T) results in the expression fact that the number of free moles nB corresponds to the num-
ber of freely moving particles must be taken into consideration.
FH 1 FH T
T0 If, however, nB moles dissociate into z smaller particles in solu-
a
b  a b
1

lnxA  (6) tion, then the number of actually existing moles is
R T0 T1 R TT0
n = nB (1 + (z 1) a) (12)
As the freezing point depression FT = T T0 is small compared
where a is the degree of dissociation.
with T0 the term TT0 can be replaced with T02. If the amount xB
Under certain conditions, the determination of molar masses
of the solute is considered concurrently, then xA can be replaced
using ebullioscopy can therefore only supply the apparent molar
with 1 - xB. This results in
mass Ms which has then to be converted using
FH T
T0
a b 
ln 11
xB 2 (7) MB
Ms 
11  1z
12 a2
R T20 (13)

Equation (7) can be developed as a series:

When concentrations are higher, the interionic interactions of the
FH FT 1 2 1 existing ions must also be taken into account. The osmotic coef-
 xB  xB  x3B ... (8)
RT20 2 3 ficient f0 is used to describe this interaction. This has a value
between 0 and 1 for real solutions and a value of 1 for ideal solu-
When xB is small, only the first linear term needs to be consid- tions.
ered. The freezing point depression then reduces to
n = nB (1 + (z f0 1) a) (14)
R T20
FT  xB (9) The effective amount of substance in the solution differs from the
FH
value used by an amount equal to the Vant Hoff Factor i =
In dilute solutions, the amount of substance can be expressed (1 + (z f0 1) a). It therefore follows analogously that the exper-
as a good approximation by the quotients (mBMA / mAMB). MA, imentally determined freezing point depression is greater than
MB and mA, mB are the molar masses and the weighed masses the theoretical value calculated from the weighed amounts by a
of solvent A and solute B respectively. factor i.

R T20 mBMA R T20 MA mB

FT   (10)
FH mAMB FH mAMB Data and results
Kc (water) = 1.86 K kg mol-1
The apparent molar mass of table salt was experimentally deter-
Finally, the fraction mB / mAMB is equal to m / 1000, in which m mined to be 29.58 g mol-1.
represents the molality, i.e. the amount of solute in 1000 g of sol- The literature value is 58.443 g mol-1. Consequently, for a = 1
vent. and f0 = 1 a dissociation ratio of 1:2 results.
R T20 MA m Molar mass of hydroquinone (in g mol-1; a = 0): 106.87 (exp.);
FT   Kc m (11) 110.11 (lit.).
FH 1000

PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen P3021101 3
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Freezing point depression
02.11

4 P3021101 PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen