Exp 22

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Title: Cryoscopy: Determination of Relative Molecular Mass by Endpoint Cryoscopy

Objectives:
a) To determine the relative molecular mass of unknown compound by endpoint
cryoscopy
b) To determine the freezing point depression constant when naphthalene dissolved in
DMSO.
Results:
Mass of naphthalene=1.0035g
Temperature measured for DMSO (°C)
Time (s)
Part A Part B Part C
0 23.0 25.0 24.0
30 22.0 18.0 20.0
60 20.0 15.0 16.0
90 19.0 14.0 13.0
120 18.0 14.0 11.0
150 18.0 14.0 10.0
180 18.0 13.0 9.0
210 18.0 13.0 8.5
240 18.0 12.0 8.0
270 18.0 12.0 8.0
300 18.0 11.5 8.0
330 18.0 11.0 8.0
360 17.5 11.0 8.0
390 17.5 11.0 8.0
420 17.5 11.0 8.0
450 17.5 11.0 8.0
480 17.5 11.0 7.0
510 17.5 11.0 7.0
540 17.5 11.0 7.0
570 17.5 11.0 6.5
600 17.5 10.5 6.0
630 17.5 10.5 6.0
660 17.5 10.5 6.0
690 17.0 6.0
720 17.0 5.5
750 17.0 5.0
780 17.0 5.0
810 17.0 5.0
Part A:

Graph of temperature against time


25

20
Temperature (⁰C)

15

10

0
0 100 200 300 400 500 600 700 800 900
Time(s)

Graph 1: Temperature of Pure DMSO After Taken Out from Ice Water Bath
Part B:

Graph of temperature against time


30

25

20
Temperature(⁰C)

15

10

0
0 100 200 300 400 500 600 700 800 900
Time (s)

Graph 2: Temperature of DMSO with Dissolved Naphthalene After Taken Out from Ice
Water Bath
Part C:

Graph of temperature against time

30

25
Temperature(⁰C)

20

15

10

0
0 100 200 300 400 500 600 700 800 900
Time (s)

Graph 3: Temperature of DMSO with Dissolved Unknown Liquid After Taken Out from
Ice Water Bath
Calculations:
From graph 1:
The freezing point of DMSO, T1= 17.5°C
From graph 2:
The freezing point of DMSO + naphthalene, T2= 11.0°C
From graph 3:
The freezing point of DMSO + unknown liquid , T3= 8.0°C
B:Determination of cryoscopic constant of DMSO, k
Density of DMSO=1.10g/cm3
Mass of 20mL of DMSO =20 cm3 x 1.10g/cm3
= 22g
W (naphthalene)/ 1000g = 1.0035g /22g
W(naphthalene)= 45.6136g
M (naphthalene) = 128.3g/mol
∆T = T1 – T2
= 17.5K-11.0K
= 6.5K
∆T= k[W(naphthalene)/M(naphthalene)]
6.5K = k[45.6136g/128.3g/mol]
k= 18.2829 Kmol-1
C: Determination of relative molecular mass of unknown liquid
Density of unknown liquid= 0.962 g/cm3
Mass of 2mL unknown liquid = 2cm3 x 0.962 g/cm3
= 1.924g
W (unknown liquid)/ 1000g = 1.924g /22g
W (unknown liquid) = 87.4545g
∆T = T1 – T3
= 17.5K-8.0K
= 9.5K
∆T= k[W(unknown liquid)/M(unknown liquid)]
9.5K = (18.2829Kmol-1)[(87.4545g/ M(unknown liquid)]
M(unknown liquid)= 168.3076g/mol

The unknown liquid is 1-dodecane.


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 was 18.5C while the freezing point obtained through experiment was 6.5C.
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 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. (Peter, n.d.)
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 non electrolyte.
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.(Bernard, 2015)
The possible error that occurred in the experiment 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. (Rsc.org,2017)
The precaution steps of the experiment that may be taken is to rinse the pipette and boiling
tube with DMSO before pipetting the unknown liquid. This is to ensure the pipette and
boiling tube inside no water droplets which will affect the entropy. 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. Make sure the apparatus were properly
cleaned before starting the experiment. Make sure the liquid in the boiling tube is evenly
stirred when the temperature was taken and recorded. Wear gloves and goggles when
carrying out the experiment to ensure safety. Make sure the line of vision is parallel to the
level of pipette to prevent parallax error while measuring the volume of solution.
(Llanov.webpda.info,2018).
Conclusion:
The cryoscopic constant for this experiment is18.2829 Kmol-1. The relative molecular mass
of the unknown liquid was about 168.3076g/mol. The unknown liquid is 1-dodecane.

References:
1. Bernard, L.(2015). Experiment Men 22 .[online] Scribd. Available at:
https://www.scribd.com/document/262028455/Experi-Men-22 /html[Accessed 16 Apr.
2015].
2. Peter, H.(n.d.). Experiment 4 Solution and Melting Point. [online] Available at:
https://www.scribd.com/document/18026453/Exp-4/html.
3. Llanov.webpda.info. (2018). Cryoscopic determination of relative molecular mass by
endpoint cryoscopy [online] Available at: http://llanov.webpda.info/2/ [Accessed 15 Feb.
2018].
4. Rsc.org. (2017). Determining relative molecular masses by weighing gases- Learn
Chemistry. [online] Available at: http://www.rsc.org/learn- chemistry/resource/
res00000832/determining-relative-molecular-masses-by-weighing-
gases?cmpid=CMP00005011/html [Accessed 2017].
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 non electrolyte.
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 on 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.

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