Experiment: 22

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 inDMSO. Determine the relative molecular
mass of an unknown liquid from the freezing depression constant.
Introduction:
Freezing point depression is one of the colligative properties of solution, meaning thatthis
property is universal to all solutes in all solution regardless the identities of
thesolvent 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 andtheir
quantities.When there is solute dissolved in a solvent forming a solution, the freezing point of
thesolution is lower than the pure solvent due to the presence of added solute. Freezing
pointdepression in a solution is due to the entropy of the solvent in different phases. Entropy
isthe 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, whichmean both phases are energetically equivalent. However, the entropy
is temperaturedependent, the higher the temperature, the higher the entropy. The solute is
dissolved inthe liquid rather than in solid, this causing the entropy of liquid phase is lowered by
thedilution while the entropy of solid phase is unaffected. In the presence of solute,
theequilibrium temperature between solid-liquid phases is shifted or more precisely loweredto
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 themole 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. Athigher
concentration of solute in solution, the above equation will be less accurate due toderivation
from ideality.

Apparatus and Materials :

Boiling tube, salt / ice / water bath, stopwatch, thermometer (-20 C to + 30 C, graduated in 1 /
10 C), stirrer, 20 cm3 and 2 cm3 pipettes (both fitted with suction bulb), benzene, naphthalene,
unknown liquid.

Experimental Procedure

Benzene is used as the solvent in this experiment because it is readily available, possesses a
convenient freezing point, and has a relatively large cryoscopic constant.

a) Determination of freezing point of pure solvent. Pipette exactly 20 cm3 of benzene into a
pyrex boiling tube and cool it in a salt / ice / water bath until about one half of it has
frozen. Then clamp it vertically, insert a (1 / 10 C) thermometer, stir gently and note the
temperature at 1 / 2 minute intervals until all the solid has melted and then for a further 3
minutes. The melting portion of the (temperature versus time) curve should be flat for a
pure substance.

b) Determination of cryoscopic constant of benzene. The freezing point of pure benzene (T0)
is obtained in (a). Add an accurately known mass of naphthalene (ca. 1.0 g) to the 20 cm3
of benzene used in (a) and determine the melting curve for the solution as described in
(a).

c) Determination of relative molecular mass of unknown compound. Pipette exactly 2 cm3

of the unknown liquid into a boiling tube containing exactly 20 cm3 of benzene.
Determine the freezing point of this solution as described in (a) ( = Tu).

Results:
*Table 1: Temperature of Pure DMSO After Taken Out from Ice Water Bath
Time(minute)
Temperature(c)
4.5
11.0

5.0
12.0

5.5
12.0

0.0
12.0

0.5
11.0

1.0
10.0

1.5
9.0

6.0
12.5

6.5
13.0

7.0
14.0

7.5
14.0

2.0
9.0

2.5
9.0

3.0
9.0

3.5
9.0

4.0
10.0

Table 2: Temperature of DMSO with Dissolved Naphthalene After Taken Out from Ice Water
Bath
Time(minute)
0.0
Temperature(c) 5.0
4.5
8.5

5.0
9.5

0.5
4.5

1.0
4.5

1.5
5.0

2.0
5.0

2.5
5.0

3.0
6.0

3.5
7.0

4.0
8.0

5.5
10.0

Table 3: Temperature of DMSO with Dissolved Unknown Liquid After Taken Out from Ice
Water Bath
Time(minute)
0.0
Temperature(c) 17.0

0.5
16.0

4.5
13.5

5.0
13.5

5.5
13.5

6.0
14.5

10.0
21.0

10.5
21.0

11.0
21.0

11.5
21.0

1.0
15.0
6.5
15.0

1.5
15.0
7.0
15.0

2.0
14.0
7.5
16.0

2.5
14.0
8.0
17.0

3.0
14.0
8.5
18.5

3.5
13.5
9.0
19.0

4.0
13.5
9.5
20.5

Result considered failure; standard freezing point of MDSO will be obtained fromanother 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

Calculation :Part 1. Determination of Freezing Point of Pure DMSO from the graph obtained
from table 1, the freezing point of pure MDSO is 9.0C, but this significantly
fluctuated from the theoretical freezing point of the pure MDSO.Therefore, standard freezing
point is used. Freezing point of DMSO = 18.5C [2]Part 2. Determination of Cryoscopic
Constant Density of DMSO = 1.1 g/cm3 at 20C, 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 DMSOM (naphthalene) = 128.3 g/mol Freezing point of
DMSO with dissolved naphthalene = 5.0c Freezing point depression = (18.5 5.0)oC = 13.5C
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 20C, Volume of
unknown liquid=2 cm3
Mass of unknown liquid used = (0.947 x 2) g= 1.894 gW (unknown) = 114.7879 g per 1000 g of
DMSO Freezing point of DMSO with unknown liquid = 13.5oCFreezing point depression =
(18.5 13.5)oC= 5.0C
T=k[Wunknown Munknown]5.0=269.36[114.7879Munknown]
M (unknown) = 6183.85Relative 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 18.5C [2] while the freezing point obtained through experiment was
9.0C. The freezing point of pure DMSO obtained was lower than
thefreezing 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,
thenremain constant followed by increased. U-shaped graphs were obtained rather thantheoretica
l 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 4.5C, but the temperature remains constant again from minute 1.5 to minute 2.5 at
5.0C. 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 1and 3. The temperature of solution should be
remained constant before the solid phasewas disappeared due to the solidliquid equilibrium when the freezing point wasachieved. 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 subs
tances 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:
-PETER HONG LEONG CHEAH. Exp 4. [online]. Exp 4. Available at:
-https://www.scribd.com/doc/18026453/Exp-4. Use on 1st april 2015.

UDEC 1134
CHEMISTRY LABORATORY 1

NAME

BERNARD CHEONG JIA CHOON

NAME OF GROUP MEMBERS

TANG YI ZHANG, PAN WAI SENG

STUDENT ID

1406645

NO. OF EXPERIMENT

EXP 22

TITLE OF EXPERIMENT

Cryoscopy: Determination of relative

molecular by endpoint cryoscopy

DATE OF EXPERIMENT

6/04/2014

PRACTICAL GROUP

P2

LECTURER

MS CHANG CHEW CHEEN