University of Santo Tomas

Faculty of Engineering
Chemical Engineering Department

ChE321L Experiment No. 3

DETERMINATION OF THE
MOLECULAR WEIGHT OF A
NON-VOLATILE SOLID BY
THE CRYOSCOPIC METHOD
Prepared by:
GROUP No. 3
LUNK, Michael Angelo
YUSON, Joana Marie N.
I. INTRODUCTION
The objective of this experiment
is to determine the molecular
weight of an unknown solute using
the cryoscopic method or freezing
point depression method.
 The general definition of freezing
point depression is the effect of
lowering the freezing point of a
substance due to an increased
amount of solute added to the
solvent. This principle can be
explained in three primary equations.
 These are:

Equation 1 ΔTf = Tpuresolvent - Tsolution

Equation 2 Kf = ΔTf MWsolute msolvent /
msolute
Equation 2 can also be rearranged to Equation 3
Equation 3 MWsolute = Kf msolute /ΔTf
msolvent
 The Cryoscopic constant, Kf (of Glacial
acetic acid) was determined. We first
determined the freezing point of the pure
glacial acetic acid, and then the freezing point
of the solutions containing measured masses
of glacial acetic acid and benzoic acid. From
these experimental data, we have calculated
the Kf of Glacial Acetic Acid.
 We have prepared a solution of
known masses of an unknown
substance dissolved in the Glacial
acetic acid and and determined the
freezing point of the solution. From
these data, we have calculated the
molar mass (MW) of the unknown
substance.
 After the experiment, it
was realized that the H+ ions
within the solutes used have
played a big role in the
freezing point depression of
the solution.
II. PROCEDURE
A. Determination of Cryoscopic Constant of the Solvent

Crushed Ice
1. PLACED in the beaker
15mL Glacial Acetic Acid
2. TRANSFERRED in the hard glass
test tube 3. DIPPED in the ice-water
mixture
4. RECORDED temperature
reading
All contents SOLIDIFIED (15 seconds interval)
5. TRANSFERRED into an empty
beaker
6. RECORDED temperature reading
All contents (15 seconds interval)
LIQUEFIED
 Crushed Ice
1. PLACED in the
15mL Glacial Acetic Acid
beaker
2. TRANSFERRED in the hard glass
test tube 3. ADDED with 1-2 grams
Benzoic Acid
4. STIRRED
Benzoic
Acid is
Completel
y 5. DIPPED in the ice-water
Dissolved
mixture
All contents SOLIDIFIED 6. RECORDED temperature
reading
7. TRANSFERRED into an empty beaker
(15 seconds interval)
8. RECORDED temperature reading
(15 seconds interval)
All contents
LIQUEFIED *This procedure was done twice using
varied masses of Benzoic Acid (between
1.0g -1.5g) and a new volume of Glacial
Acetic Acid
 B. Determination of the Molecular Weight of the Unknown Solute

Crushed Ice
1. PLACED in the beaker
15mL Glacial Acetic Acid
2. TRANSFER in the hard glass
test tube 3. ADDED with 1-2 grams unknown
solute
UNKNO4. STIRRED
WN
SOLUTE
5. DIPPED in the ice-water mixture
6. RECORDED temperature reading
(15 seconds interval)
All contents SOLIDIFIED
*This procedure was
7. TRANSFERRED into an empty beaker
done twice using varied
8. RECORDED temperature reading
masses of unknown
(15 seconds interval) solute (between 1.0g
All contents -1.5g) and a new volume
LIQUEFIED of Glacial Acetic Acid.
III. DATA AND
RESULTS
 A. DETERMINATION OF THE CRYOSCOPIC CONSTANT
OF THE SOLVENT
Table 1. Temperature readings to determine the freezing point
the pure Acetic Acid (Tsolvent ) and Acetic-Benzoic Acid solutions (Tsolution )
Mixture t/mm:s T/°C Observation
s
15mL Pure 01:30 15 First Crystals
Glacial Acetic appeared
Acid 14:45 15.5 Pure solid
(01:)
17 Pure liquid
00:45
15mL Pure 02:00 10 First Crystals
Glacial Acetic appeared
Acid+1.4100 g 18:30 12.5 Pure solid
Benzoic Acid 42:30 17 Pure liquid
* Freezing
10mL Point
Pure 01:45 9 First Crystals
 Pure liquid
Temperature (°C)

Pure solid

Liquid - solid
First crystals appears

Time (minutes)

Figure 1. Cooling curve for pure Glacial

Acetic Acid.
 Pure liquid
Temperature (°C)

Pure solid
Liquid - solid

Liquid - solid
First crystals appears

Time (minutes)

Figure 2. Cooling curve for the solution of

Benzoic Acid in Glacial Acetic Acid.
 B. DETERMINATION OF THE MOLECULAR WEIGHT OF
THE UNKNOWN SOLUTE

Table 2. Temperature readings to determine the freezing poin

of the Glacial Acetic Acid- Unknown substance solutions (Tsolution
Mixture t/mm:s T/°C Observation
s
15mL Pure 02:30 12.5 First Crystals
Glacial Acetic appeared
Acid+1.2768 g 04:15 13 Pure solid
Unknown solute 37:15 18 Pure liquid

10mL Pure 01:15 11.5 First Crystals

* Freezing Point
Glacial Acetic appeared
Acid+1.3745 g 12:30 11.5 Pure solid
Unknown solute
 Pure liquid

Pure solid
Liquid - solid

First crystals appears

Liquid - solid

Figure 3. Cooling curve for the solution of

Unknown solute in Glacial Acetic Acid.
COMPUTATIONS
*The following formulae were used to obtain the
required values
m= Where:in Procedure A:
ρV  m is the mass in g.
 ρ is the density in
g/mL.
 V is the volume in
ΔTf = Tpuresolvent
mL. - Tsolution
Where:
 ΔTf is the lowering of the freezing point in
°C.
 Tpuresolvent is the freezing point of pure
solvent in °C.
 Kf = ΔTf MWsolute msolvent /
Where: msolute
 Kf is the cryoscopic constant in °C kg/
mole.
ΔTf is the lowering of the freezing point in
°C.
 MWsolute is the molecular weight of solute
in*The
°C. following formulae were used to obtain the
 msolvent is the mass of solvent
required values in kg.
in Procedure
 msolute is the mass of soluteB:
in g.- T
m= ΔT = T f puresolvent solution
ρV
MW = Kf msolute /ΔTf
solute

msolvent
 A. DETERMINATION OF THE CRYOSCOPIC
CONSTANT (Kf) OF THE GLACIAL ACETIC ACID
• MWsolute : MW C 6H5COOH = 122 g/mole
• Tpuresolvent : T CH 3COOH = 15.5 °C (from Table 1)
• ρsolvent : ρ CH 3COOH = 1.049 g/mL
(from Atkin’s Data Section on page 990)

TRIAL 1
• m C 6H5COOH = 1.4100 g
• V CH 3COOH = 15 mL;
• Tsolution = 12.5 °C (from Table 2)
since m= ρV, then
• m CH 3COOH = 0.015735 kg

ΔTf = Tpuresolvent – Tsolution = 15.5 °C - 12.5

°C
ΔTf = 3 °C
 • ΔTf = 3 °C
• MWsolute = 122 g/mole C6H5COOH
• msolvent = 0.015735 kg CH3COOH
• msolute = 1.4100 g C6H5COOH
Kf = ΔTf MWsolute msolvent
msolute
= 3 °C (122 g C6H5COOH /mole C6H5COOH ) (0.015735 kg CH 3COOH

1.4100 g C6H5COOH

Kf(Trial 1) = 4 °C kg/mole
 A. DETERMINATION OF THE CRYOSCOPIC
CONSTANT (Kf) OF THE GLACIAL ACETIC ACID
• MWsolute : MW C 6H5COOH = 122 g/mole
• Tpuresolvent : T CH 3COOH = 15.5 °C (from Table 1)
• ρsolvent : ρ CH 3COOH = 1.049 g/mL
(from Atkin’s Data Section on page 990)

TRIAL 2
• V CH 3COOH = 10 mL;
• m C 6H5COOH = 1.4916 g
since m= ρV, then
• Tsolution = 11 °C (from Table 3)
• m CH 3COOH = 0.01049 kg

ΔTf = Tpuresolvent – Tsolution = 15.5 °C - 11

°C
ΔTf = 4.5 °C
 • ΔTf = 4.5 °C
• MWsolute = 122 g/mole C6H5COOH
• msolvent = 0.01049 kg CH3COOH
• msolute = 1.4916 g C6H5COOH
Kf = ΔTf MWsolute msolvent
msolute
= 4.5 °C (122 g C6H5COOH /mole C6H5COOH ) (0.01049 kg CH 3COOH

1.4916 g C6H5COOH

Kf(Trial 2) = 3.86 °C kg/mole

 Average Kf :

Kf(Trial 1) = 4 °C +
Kf(Trial 2) = 3.86 °C kg/mole
= kg/mole
2

Kf=(Average) = 3.93 °C kg/mole

 B. DETERMINATION OF THE MOLECULAR WEIGHT
OF THE UNKNOWN SOLUTE
• Kf = 3.89 °C kg/mole
• Tsolvent : T CH 3COOH = 15.5 °C (from Table 1)
• ρsolvent : ρ CH 3COOH = 1.049 g/mL
(from Atkin’s Data Section on page 990)

TRIAL 1
• m unknown = 1.2768 g
• V CH 3COOH = 15 mL;
• Tsolution = 13 °C (from Table 4)
since m= ρV, then
• m CH 3COOH = 0.015735 kg

ΔTf = Tsolvent – Tsolution = 15.5 °C – 13 °C

ΔTf = 2.5°C
 • ΔTf = 2.5 °C
• Kf = 3.89 °C kg/mole
• msolvent = 0.015735 kg CH3COOH
• msolute = 1.2768 g unknown
MWsolute = Kf msolute
ΔTf msolvent
= 3.93 °C kg CH 3COOH /mole unknown (1.2768 g unknown )
2.5 °C (0.015735 kg CH 3COOH )

Mwunknownsolute (Trial 1) = 127.56 g/mole

 B. DETERMINATION OF THE MOLECULAR WEIGHT
OF THE UNKNOWN SOLUTE
• Kf = 3.89 °C kg/mole
• Tsolvent : T CH 3COOH = 15.5 °C (from Table 1)
• ρsolvent : ρ CH 3COOH = 1.049 g/mL
(from Atkin’s Data Section on page 990)

TRIAL 2
• m unknown = 1.3745 g
• V CH 3COOH = 10 mL;
• Tsolution = 11.5 °C (from Table 4)
since m= ρV, then
• m CH 3COOH = 0.01049 kg

ΔTf = Tpuresolvent – Tsolution = 15.5 °C – 11.5 °C

ΔTf = 4°C
 • ΔTf = 4 °C
• Kf = 3.93 °C kg/mole
• msolvent = 0.01049 kg CH3COOH
• msolute = 1.3745 g unknown
MWsolute = Kf msolute
ΔTf msolvent
= 3.93 °C kg CH 3COOH /mole unknown (1.3745 g unknown )
4 °C (0.01049 kg CH 3COOH )

Mwunknownsolute (Trial 2) = 128.74 g/mole

 Average Molecular Weight :

+ (Trial2)
MW (Trial1) = 127.56 MW = 128.74 g/mole
= g/mole
2

MW
= Unknownsolute (Average) = 128.15 g/mole
 IV. PERCENT ERROR
PERCENT ERROR = | Experimental – Theoretical |
Theoretical
Average Kf:
% error = |3.93 °C kg/mole – 3.9 °C X 100
kg/mole|
3.9 °C kg/mole
% error = 0.77 %

Average Molecular Weight :

% error = |128.15 g/mole – 128.1632 g/mole|
X 100
128.1632 g/mole
% error = 0.01 %
 V. ANSWERS TO
QUESTIONS
1. From the plot of
temperature vs. time, the
freezing point can be
determined by observing the
lowest point on the curve. It is
the indication when freezing is
nearly to occur.
2. Based on the results, the
freezing point of pure acetic acid
is relatively higher compared to
the solutions’ freezing point after
a certain amount of solute is
dissolved in the acetic acid. As
the solvent crystallizes, the solute
concentration increases, resulting
in further lowering of freezing
temperature.
3. The calculated molecular
weight of the unknown solute
was not affected by the amount
of acetic acid used. Instead, it is
the freezing point that was
affected by the amount of the
acetic acid.
ΔTf =ThisKcan
f m be
solute
proven
by the equation:
MW m
solute solvent
So if the amount of glacial
acetic acid used was more
than 15mL, then the freezing
temperature would have
become higher and lower if it
was less than 15mL.
4. If one is to guess what the
solid sample is without looking
at the result of the experiment,
the first logical clue that must
be considered is its smell since
all the solidified solutions in
this experiments looks the
same.
5. Supercooling is a
phenomenon where in a liquid
cools below its freezing point
before crystallization occurs.
This phenomenon has actually
occurred in all parts of this
experiment as explained in the
graphs.
VI. CONCLUSION AND
RECOMMENDATION
In the addition of the
naphthalene to the Glacial acetic
acid solution. The H + ions within
the naphthalene cause the
freezing point to lower because
the ions act to disrupt the bonds
between the particles.
 The percent error was calculated
to be relatively low (around 0.01%).
Errors that contributed to this could
include impurities in the Glacial
acetic acid-naphthalene mixture and
imprecise readings of temperature
and masses of substances.
REFERENCES
*Atkin’s Physical Chemistry 8th Edition
*Physical Principles 2 Laboratory Manual
*Leider’s Physical Chemistry 3rd Edition
*http://www.ncbi.nlm.nih.gov/pmc/articles/PMC125
3340/pdf/biochemj01101-0190.pdf
*http://www.chemistry.ccsu.edu/glagovich/teachin
g/31
Thank you for
listening! 
 Definition of Terms
 CRYOSCOPY - A phase-equilibrium
technique to determine molecular
weight and other properties of a
solute by dissolving it in a liquid
solvent and then ascertaining the
solvent's freezing point.