Determining Molar Mass using Cryoscopy

Valentin Uzunov (author) & Francesca Frattaroli (lab partner)

PSU ID#: 964100377
CHM 228H, Lab 261


ABSTRACT
The freezing point depression of a pure liquid and a solution of the liquid can be used to detemine
the molar mass of the solute in solution. In the following experiment the molar mass of
acetylsalicylic acid (ASA) was determine by cryoscopy of t-butanol. The freezing point of pure t-
butanol was measured at 17.34 C 1.96 (2sd) with 32.0 % error difference from literature given
values. The addition of 0.132g of ASA to t-butanol resulted in a freezing point depression of
3.25 C. An additional 0.100g of ASA produced a further decrease of 1.36 C. From the freezing
point depressions of each solution the mean molar mass of ASA was calculate as 174.47 g/mol
94.12 (2 sd), a 3.16% error difference from literature value. The aggregate results determined the
molar mass of ASA to be 208.16 g/mol, a 13.5% error difference.


INTRODUCTION
The measure of the difference between freezing points of a pure solvent and a solution of that
solvent is called cryoscopy. In the following experiment the freezing points of pure liquid t-butanol
and two different concentration solution of t-butanol with a known mass of acetylsalicylic acid
(ASA) dissolved were experimentally measured. From the expected freezing point depression the
molar mass of ASA was then calculated. To achieve a good approximation to the true molar mass
of ASA is expected to be highly dependent on the accuracy and precision of the change in freezing
points between solutions and pure liquid.
When a solute is dissolved in a pure solvent, the freezing point of the solution is lowered compared
to the freezing point of the pure solvent alone, this phenomenon is known as freezing point
depression. Freezing point depression (FPD), melting point elevation, vapor pressuring lowering
and osmotic pressure are properties of solutions whos magnitude dependent upon the ratio of
solute to solvent particles in the solution. Collectively these properties make up the colligative
properties of a solution. Colligative properties are most often studied in dilute solutions whose
behavior can be often approximated to that of an ideal solution. Because of this, the chemical nature
of the solute and solvent and their interactions can be considered as being negligible. The
expression that describes this relationship is:

[Eq 1]
Where T the change in freezing point between the pure solvent and a solution of the solvent of m
(molal) concentration. i is the vant Hoff factor, and K
F
is the freezing point depression constant of
the solvent. Notice that because molality of a solution is independent of temperature, the
concentration and the K
F
does not change with temperature.

When a liquid is cooled sufficiently so that the thermal energy of constituent molecules is
insufficient to overcome the IMF, the rate of crystallization becomes favored and the liquid begins
phase change from liquid to solid as it crystalizes. At the freezing point of the solvent, the liquid
and solid phases reach dynamic equilibrium. At this point the freezing point of the system can be
expressed as:

Eq 2]
Where T
f
is the freezing point, H is the enthalpy of system and S is the entropy of the system.
[Eq 2] shows that there is an inverse relationship between the entropy of a system and its freezing
point. Thus when a solute is added to a pure solvent, the absolute change in entropy of the solution
becomes greater than for the pure solvent, reducing the freezing point. It should be noted that at
dilute concentration of solute, it can be assumed, due to the ideal behavior approximation, that the
absolute change in enthalpy will be negligible.
An important factor to consider when for all colligative properties is the vant Hoff factor, which is
a is a measure of the effect a solute will have on the magnitude of the property. The vant Hoff
factor is a ratio between the molar concentrations of particles in solution and the molar
concentration of the solute taking into account ion dissociation that takes place in solution:



[Eq 3]
For non-polar, non-electrolytes substance dissolved in solvent a polar solvent like water, the vant
Hoff factors is 1. Each formula unit counts as an individual particle. However for ionic compounds
the dissociation into ions must also be accounted. The vant Hoff factor for ideal solution assumes
dissociation that an ionic or polar compound completely dissociates. Experimentally however the
vant Hoff factor for a solution will deviate from the whole number approximation due to a small
percentage of ion-paring that occurs to some extent in all electrolyte solutions. This deviation tends
to be greater with ions which have multiple charges. In the current experiment the vant Hoff factor
was assumed to be equal to 1. Both ASA and t-butanol are miscible without any significant
dissociation, thus each ASA molecules will count as one individual particle in solution, and the
magnitude of the freezing point depression will be thus related to the mass of the solute in solution
The success of the experiment was expected to be largely dependent on the accuracy and precision
of the freezing points measures. Two methods were used to estimate the freezing point:
approximation from graphical data, and bisection of lines of best fit from data. Both methods are
believed to be valid, and were used to estimate the freezing points measured.

DATA

Table 1- Measured freezing points of pure t-butanol and two different molal concentration solutions
with acetylsalicylic acid
Mass
test-
tube (g)
Mass
t-butanol
& Test
Tube (g)
Mass of
t-butanol
(g)
T
f
t-
butanol
(C )
Mass of t-
butanol
and ASA 1
(g)
T
f
t-
butanol &
ASA 1
( C )
Mass of t-
Butanol
and ASA 2
(g)
T
f
t-
butonol &
ASA 2
( C )
7.765 9.928 2.163 17.47 10.06 13.67 10.161 13.0
18.04 14.57 12.5
16.13 14.02 12.7









Table 2- Shows aggregate measurements of mean molar mass of acetylsalicylic acid
First addition of
ASA
Second addition of
ASA
Mean
MW (g/mol) MW (g/mol)
155.32 193.62 174.470
206.44 189.80 198.120
290.53 283.31 286.920
291.14 236.58 263.860
172.12 193.93 183.030
219.80 272.72 264.260
67.61 163.12 115.370
246.55 132.06 189.310
166.86 229.31 198.090


RESULTS & DISCUSSION

Table 3 Summarizes the experimental data and results of experiment
Solution
Mass
Solute
(kg)
Mass
solvent
(kg)
T
f
(C)
Mean Sd
T (C
Sd)
molals
(mol/kg )
mols of
solute
(mol)
MW of
ASA Sd
(g/mol)
t-butanol 0 0.002163
17.34
0.980
0 1 0
t-bunanol
and ASA 1
0.000132 0.002163
14.09
1.08
3.25
1.08
0.393
1.01
0.000850
155.32
51.6
t-bunanol
and ASA 2
0.000233 0.002163
12.73
1.01
4.61
1.01
0.556 0.00120
193.62
42.5

The results of the current experiment displayed in Table 3, show a freezing point depreciation of the
between pure solvent and solvent solutions, depedent on mass of solute. The addition of 0.132g of
ASA to t-butanol resulted in a freezing point depression of 3.25 C with an additional 0.100g of
producing a further decrease of 1.36 C. The addition of solute to the solvent shows a diminishing
effects on the lowering the freezing point.


Figure 1 - Figure shows the change in temperature of pure t-butanol with respect to time as it is cooled. Freezing is
indicated by the near horizontal slopes on the curves. Freezing point marks the beginning of this region.
The graph in figure 1 demonstrates the change in temperature of pure t-butanol as it is cooled.
Ideally at the freezing point is marked when the rate of the temperature change is 0, followed by a
constant temperature region, until all liquid freezes, followed by a cotinued lowering of substances
temperature. Data collected did not show this ideal behavior, however a noticeable decrease in the
rate of cooling was mreasured. The mean freezing point of t-butanol at STP, was measured to be
approximately 17.34 C 1.96 (2sd). The freezing point of t-butanol is listed in literature [1] as
being between 25-26 C [1], a 32.0 % error difference from current measurements.

Figure 2 Figure 2 show a drop in freezing point between pure t-butanol compared to 2 different molar solutions of t-
butanol and acetylsalicylic acid (ASA)
Figure 2 clearly shows the meaured decrease in different freezing points (marked by the intersection
of the lines) of measured solution concentrations. The freezing was estimated using bisection of
13
15
17
19
21
23
25
27
29
31
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
T
e
m
p
e
r
a
t
u
r
e

(

C
)

Time (min)
Trial 1
Trial 2
Trial 3
8
13
18
23
28
33
0.00 0.50 1.00 1.50 2.00 2.50
T
e
m
p
e
r
r
a
t
u
r
e

(

C
)

Time (min)
ASA 1
ASA 2
t-butanol
lines of best fit through lowest and highest gradient slope regions. In comparison to approximation
by visual estimation both method were determine to be effective with minimal difference in values
obtained. Either result would have produced similar results, but for simplicity, the visual estimation
form the graphical graphical data was used in subsequent calculations.

Using [Eq. 1] and referencing the known value for K
F
for t-butanol
,
the mean molar weight of
acetylsalicylic acid was determined to be 174.47 g/mol 94.12 (2 sd). The liteture molar weight of
ASA (C
9
H
8
O
4
) is given as 180.16 g/mol [2], a 3.16% error difference from current results. The
aggraget data results show the mean molar mass of the ASA to be 208.16 g/mol, which is a 13.5%
error difference from true value. As anticipated the accuracy in determining the molar mass is
largely dependent on the precision and accuracy of data collected. The inaccuracy in the results
originates largely from the freezing point depression measured relative the freezing point of pure t-
butanol and the K
F
of t-butanol. The freezing point depression in ASA1 trial was to large relative to
the K
F
, leading to an underestimation of the molar mass of ASA, and to small in ASA 2 trial,
resulting in an over estimation of ASA molar mass. The precision of the freezing point depression in
relative to the pure solvent is crucial measurement in obtaining good accuracy and low variability
and from data.


CITATION
[1] Tert-Butyl alcohol. (2013, December 17). In Wikipedia, The Free Encyclopedia. Retrieved
20:45, March 1, 2014, from http://en.wikipedia.org/w/index.php?title=Tert-
Butyl_alcohol&oldid=586470777
[2] Aspirin. (2014, February 20). In Wikipedia, The Free Encyclopedia. Retrieved 20:46, March 1,
2014, from http://en.wikipedia.org/w/index.php?title=Aspirin&oldid=596403080

















CALCULATIONS