Universiti Tunku Abdul Rahman (Kampar Campus)

Faculty of Science, Engineering, and Technology

Bachelor of Science (Hons) Biotechnology

Year 1 Semester 2

Laboratory 1B (UESB 1212)

(II) The Properties of Matter

Lecturer: Ms. Chew Yin Hoon

Student’s Name: Cheah Hong Leong

Student’s ID: 08AIB03788

Partner’s Name: Chong Shi Fern

Partner’s ID: 08AIB02580

Experiment No. 4

Title: Determination of Relative Molecular Mass by Endpoint Cryoscopy.

Date: 27 February 2009

Title: Determination of Relative Molecular Mass by Endpoint Cryoscopy

Objective:
– Determine the freezing point of Dimethyl Sulfoxide (DMSO).
– Determine the freezing point depression constant when naphthalene dissolved in
DMSO.
– Determine the relative molecular mass of an unknown liquid from the freezing
depression constant.
Theory and Background:
Solution is the special type of mixture where the mixing between the solvent and solute
are only at molecular level. The formation of solution only possible when the free energy
of the solution is favored, that means the free energy of solution is lower than that of the
pure solvent.
Freezing point depression is one of the colligative properties of solution, meaning that
this property is universal to all solutes in all solution regardless the identities of the
solvent and solute. It also regardless whether the solute is electrolyte or nonelectrolyte.
The freezing point depression is only dependent on the presence of solute in solvent and
their quantities.
When there is solute dissolved in a solvent forming a solution, the freezing point of the
solution is lower than the pure solvent due to the presence of added solute. Freezing point
depression in a solution is due to the entropy of the solvent in different phases. Entropy is
the measurement of the disorder dispersal of energy and matter. Liquid phase has higher
entropy than the solid phase.

When a pure solvent melts or freezes, the solvent is in both solid-liquid phases, which
mean both phases are energetically equivalent. However, the entropy is temperature
dependent, the higher the temperature, the higher the entropy. The solute is dissolved in
the liquid rather than in solid, this causing the entropy of liquid phase is lowered by the
dilution while the entropy of solid phase is unaffected. In the presence of solute, the
equilibrium temperature between solid-liquid phases is shifted or more precisely lowered
to another temperature.
The freezing point depression can be expressed as freezing point depression constant, or
cryoscopic constant. The depression of the freezing point of solvent is proportional to the
mole fraction of the solute in solution. The freezing point depression can be expressed
based on the following equation:
∆T=k[WsoluteMsolute]

Note: ∆T = depression of freezing point (T1 – T2)

k = cryoscopic constant
 W(solute) = mass of solute per 1000 g of solvent
M(solute) = molar mass of solute (g/mol)
However, the above equation is only correct for very dilute solution which is ideal. At
higher concentration of solute in solution, the above equation will be less accurate due to
derivation from ideality.

Apparatus and Material:

– Boiling tubes
– Ice water bath
– Stopwatch
– Thermometer
– 20 cm3 and 2 cm3 of pipettes
– Suction bulb
– Retort stand
– Dimethyl Sulfoxide
– Naphthalene
– Unknown liquid

Procedures:
Part 1. Determination of freezing point of Dimethyl Sulfoxide
1. 15 cm3 of Dimethyl Sulfoxide (DMSO) was pipetted into a boiling tube.
2. The boiling tube containing the DMSO was immersed in the ice water bath until
half of the liquid was already frozen.
3. The boiling tube was taken out from the ice water bath and clamped onto a retort
stand.
 4. The temperature of DMSO was measured with thermometer. The temperature of
DMSO was observed and recorded every 0.5 minutes until all the frozen DMSO
had fully melted.
5. Then the temperature was further measured for another 3 minutes.

Part 2. Determination of freezing point depression constant

1. 15 cm3 of DMSO was pipetted into a boiling tube.
2. About 0.1 g of naphthalene was weight using analytical balance.
3. The naphthalene was added into the DMSO in the boiling tube.
4. The boiling tube was immersed into the ice water bath until almost half of the
solution was frozen.
5. The boiling tube was then taken out from the ice water bath and clamped onto a
retort stand.
6. The temperature of the solution was measured and recorded for every 0.5 minutes
until all the frozen solution had fully melted. Then the temperature was further
recorded for another 3 minutes.
Part 3. Determination of relative molecular mass of unknown liquid
1. 15 cm3 of DMSO was pipette into boiling tube.
2. 2 ml of the unknown liquid was pipette into the boiling tube containing the
DMSO.
3. The boiling tube was immersed into the ice water bath until half of the solution
was frozen.
4. The boiling tube was then taken out from the ice water bath and clamped onto a
retort stand.
5. The temperature of the solution was measured and recorded for every 0.5 minutes
until all the frozen solution had fully melted. Then the temperature was further
measured for another 3 minutes.
Results:
*Table 1: Temperature of Pure DMSO After Taken Out from Ice Water Bath
Time (min) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Temperature (oC) 12.0 11.0 10.0 9.0 9.0 9.0 9.0 9.0

4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5

10.0 11.0 12.0 12.0 12.5 13.0 14.0 14.0

Table 2: Temperature of DMSO with Dissolved Naphthalene After Taken Out from Ice
Water Bath
Time (min) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Temperature (oC) 5.0 4.5 4.5 5.0 5.0 5.0 6.0 7.0

4.0 4.5 5.0 5.5

8.0 8.5 9.5 10.0

Table 3: Temperature of DMSO with Dissolved Unknown Liquid After Taken Out from
Ice Water Bath
Time (min) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
 Temperature (oC) 17.0 16.0 15.0 15.0 14.0 14.0 14.0 13.5

4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5
13.5 13.5 13.5 13.5 14.5 15.0 15.0 16.0 17.0 18.5

9.0 9.5 10.0 10.5 11.0 11.5

19.0 20.5 21.0 21.0 21.0 21.0

* Result considered failure; standard freezing point of MDSO will be obtained from
another source and used to calculate the freezing point depression constant.
Note:
– Graphs were plotted based on the above tables to obtain the freezing point
– The volume of DMSO used was 15 cm3
– Mass of naphthalene used was 0.1061 g
– Volume of unknown liquid used was 2 cm3

Analysis and Calculation:

Part 1. Determination of Freezing Point of Pure DMSO
From the graph obtained from table 1, the freezing point of pure MDSO is 9.0 oC, but this
is significantly fluctuated from the theoretical freezing point of the pure MDSO.
Therefore, standard freezing point is used.
Freezing point of DMSO = 18.5 oC [2]
Part 2. Determination of Cryoscopic Constant
Density of DMSO = 1.1 g/cm3 at 20 oC, Volume of DMSO = 15 cm3
Therefore, mass of DMSO = (1.1 x 15) g
= 16.5 g
Mass of naphthalene = 0.1061 g
W (naphthalene) = 6.4303 g per 1000g of DMSO
M (naphthalene) = 128.3 g/mol
Freezing point of DMSO with dissolved naphthalene = 5.0 oC
Freezing point depression = (18.5 – 5.0) oC
= 13.5 oC
∆T=k[WnaphthaleneMnaphthalene]

13.5=k[6.4303128.3]

Cryoscopic constant, k = 269.36

Part 3. Determination of Relative Molecular Mass of Unknown Liquid

Density of unknown liquid = 0.947 g/cm3 at 20 oC, Volume of unknown liquid = 2 cm3
Mass of unknown liquid used = (0.947 x 2) g
= 1.894 g
W (unknown) = 114.7879 g per 1000 g of DMSO
Freezing point of DMSO with unknown liquid = 13.5 oC
Freezing point depression = (18.5 – 13.5) oC
= 5.0 oC
∆T=k[WunknownMunknown]

5.0=269.36[114.7879Munknown]

M (unknown) = 6183.85
Relative molecular mass of unknown liquid = 6183.85
≈ 6184
Discussion:
The freezing point of the DMSO obtained from the experiment was fluctuated from the
theoretical freezing point of pure DMSO significantly. The theoretical freezing point of
DMSO given by Wikipedia was 18.5 oC [2] while the freezing point obtained through
experiment was 9.0 oC. The freezing point of pure DMSO obtained was lower than the
freezing point of DMSO with added unknown liquid. This has been opposed the
colligative property of solution.
Due to this fluctuated result, theoretical rather than experimental freezing point had been
used to calculate the freezing point depression constant of DMSO.
The graphs obtained to determine the freezing point also show unusual shapes. In most of
the graphs, the temperatures of the solution in boiling tube were initially decreased, then
remain constant followed by increased. U-shaped graphs were obtained rather than
theoretical staircase-shaped graphs.
Besides, the graphs obtained show that the temperature increased or decreased not in
smooth way. There was always more than one constant temperature over the period of
time, causing the actual freezing point of the solution hard to be determined. For
example, in graph obtained from table 2, the solution remains constant in two part of
time. From minute 0.5 to minute 1.0, the temperature of solution remains constant at 4.5
o
C, but the temperature remains constant again from minute 1.5 to minute 2.5 at 5.0 oC.
However, the temperature that remains for the longest period of time was selected as the
experimental freezing point of the respective solution.
Another unusual phenomenon observed was the shaped of graphs obtained from table 1
and 3. The temperature of solution should be remained constant before the solid phase
was disappeared due to the solid-liquid equilibrium when the freezing point was
achieved. However in the two graphs, the temperature of solution increased rather than
remains constant even though the solid phase was still present in boiling tube
One of the possible errors that occurred was the improper method in measuring the
temperature of the liquid in boiling tube. The liquid in the boiling tube might be unevenly
stirred when the temperature of the liquid was taken and recorded.
Besides, another possible error that occurred was the accidentally addition of other
substances into pure DMSO before and while the temperature was recorded. This might
happened due to the contamination of either the pipette or the boiling tube or both. These
two apparatus might not be properly cleaned by us before and during the experiment.
Contamination in pure DMSO can leaded to big fluctuation in freezing point.
The same errors might have occurred for the measurement of depressed freezing point of
DMSO with dissolved naphthalene and unknown liquid.
The only precaution step that may be taken to prevent the above errors is to rinse the
apparatus with water and distilled water more frequently before using them to minimize
the contamination occurrence. Besides, the solution in boiling tube should be stirred all
the time while the temperature was recorded to prevent any uneven distribution of heat in
the solution.

Conclusion:
The relative molecular mass of the unknown liquid was about 6184.
The value calculated was just an approximation with significant deviation from the actual
relative molecular mass of unknown liquid.

References:
1. Siska P, E. (2006). University Chemistry. Pearson Benjamin Cumming.

2. Dimethyl Sulfoxide. (n.d.). Retrieved March 1, 2009, from

http://en.wikipedia.org/wiki/Dimethyl_sulfoxide
 3. Freezing Point Depression. (n.d.). Retrieved March 1, 2009, from
http://en.wikipedia.org/wiki/Freezing-point_depression

Encl.:
Graph in determination of freezing point of pure DMSO
Graph in determination of freezing point of DMSO with added naphthalene
Graph in determination of freezing point of DMSO with added unknown liquid
Raw data