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The principle of freezing point depression is a concept that most of us learned as youngsters. We
knew that salt being spread on roads meant that our school snow days were about over. In general
chemistry we used an empirical equation to describe this phenomenon. Later in thermodynamics
we learned that this equation was due to the chemical potential of mixing. However, what all of
these studies left unanswered was what happens to the system as we move away from the
simplifying conditions of dilute solutions and/or temperatures close to the solvent freezing point.
In this experiment we will explore the phase transition behavior of binary solutions across a
broad span of compositions and solid/liquid temperatures. We still, however, will limit ourselves
to the bounds of solubility assumed by the freezing point depression model.
Operating Assumptions:
- System is a binary solution made up of non-reactive components A & B.
- It is assumed that A & B are fully MISCIBLE when both are in the LIQUID STATE.
- It is assumed that A & B are IMMISCIBLE when both are in the SOLID STATE.
This experiment will look at mixtures of benzoic acid and transcinnamic acid. Because of their similarity, these two chemicals
readily mix with one another as liquids. This is not true,
however, when they are solids. Due to differences in their
crystal structures, the system would rather form microdomains
of pure crystalline benzoic acid and separate microdomains of
pure cinnamic acid.
COOH
trans-Cinnamic Acid
COOH
Benzoic Acid
Tm Phase Equilibrium
Tsolvent =
R (T * solvent )
x solute
H fus ,solvent
(1)
Gentry, 2013
C(liq) + B(liq)
C(S)
Tm Phase Transition
liquid C+B
T*C
Free
dep zing po
ress
i
ion nt
Melting
Temperature
We first consider what happens in the case of a classic freezingpoint-depression experiment in this case using cinnamic acid
(C) as a solvent and benzoic acid (B) as a dilute solute. At the
initial freezing point for this solution, the cinnamic acid solvent
is at equilibrium between its solid and liquid phases. On the
other hand, the dilute benzoic acid solute remains only in the
liquid state since it is not miscible in solid cinnamic acid.
Because of the entropy of mixing, increasing the concentration
of the benzoic acid solute causes the freezing point of the
cinnamic acid to decrease according to the freezing point
depression equation:
solid C,
liquid C+B
0
Mole Fraction of B
C fr
T*C
Temperature
liquid
(C + B)
eez
ing
pt
solid C,
liquid C+B
pt
zing
e
e
r
Bf
solid B,
liquid C+B
0
Mole Fraction of B
The question that remains is what happens in the middle of the compositional range. The full
phase diagram is shown below. If we start on the left side of the diagram (primarily cinnamic
acid), we see that the melting point is initially that of pure cinnamic acid. As we begin to add
increasing amounts of benzoic acid, the melting point of the cinnamic acid begins to shift to
lower temperatures according to the freezing-point-depression equation. As the amount of
benzoic acid continues to increase, the solvent melting point continues to decrease although at
some point the relationship is no longer a simple linear equation. The same set of behaviors
holds true on the right side of the phase diagram. What is obvious from the diagram is that the
two freezing-point-depression relationships must intersect at some point. This intersection is
called the eutectic point. At this point both compounds have the same freezing point and will
simultaneously solidify rather than only one compound or the other undergoing a liquid/solid
transition.
Binary Phase Diagram
liquid (C + B)
T*C
Temperature
fr e
ez
ing
pt
eutectic
point
Bf
solid C
liquid C+B
g
zin
ree
T*B
pt
solid B
liquid C+B
solid C + solid B
Mole Fraction of B
What is less obvious from the discussion above is what happens to the binary system at
temperatures below the eutectic point. Consider the diagram on the next page:
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T*B
Temperature
solid
liquid (C + B)
liquid
c
d
0
solid C + solid B
xB, total system
Mole Fraction of B
At point (a) the system is an all-liquid mixture of 0.20 benzoic acid and 0.80 cinnamic
acid. The system remains a liquid solution so long as the temperature remains above
point (b).
At point (b), according to the thermodynamics of mixing, pure cinnamic acid solvent will
begin to solidify. The remaining liquid is a mixture of cinnamic acid and benzoic acid.
Between points (b) and (c) the residual liquid is no longer at the original 20:80
composition. Since pure cinnamic acid has been lost to the SOLID phase, the
RESIDUAL LIQUID composition shifts to a higher relative fraction of benzoic acid.
This new composition generates a new, lower melting point according to freezingpoint depression theory.
As the temperature continues to drop below point (b), more and more of the cinnamic acid
converts to the solid phase, which in turn causes a continued increase in the relative
amount of benzoic acid in the remaining liquid phase. The changing liquid
consequently freezes at lower and lower temperatures according to the Tm vs.
composition transition line on the phase diagram until temperature (c) is reached.
\
At point (c) the residual liquid composition will have reached the eutectic point. If the
system is dropped in temperature below point (c) then all of the remaining liquid must
simultaneously undergo a phase transition to the solid state.
To summarize, we can look at the phase diagram in terms of holding the overall composition of the
system constant and varying the temperature. If this is the case, then moving from point (a) all the
way to point (d) shows the composite system will go through two different phase transitions:
Transition (b): Pure solvent begins to freeze. The temperature of this transition depends
on the starting composition of the overall system according to freezing-point
depression theory and the entropy of mixing. A mixed liquid of changing composition
is left behind when the solvent begins to solidify.
Transition (c): All remaining mixed liquid will freeze. The temperature of this transition
is independent of starting concentration and instead is defined by the eutectic point.
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phase
transition
d
oli
fs
o
ng
ati
he
ing
at
he
uid
liq
f
o
Temperature
phase
transition
heat capacity
of solid
heat capacity
of liquid
0
Temperature of Sample
Side View
Reference Cell
Sample Cell
reference
(empty pan)
reference cell
sample
aluminum pan
furnace block
cell mount
temperature
sensor
furnace block
sample cell
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electric
heater
electric
heater
-heat
comparator
temperature
sensor
SAMPLE PREPARATION:
Your instructor will provide you with prepared samples. These are mixtures of trans-cinnamic acid
and benzoic acid. 5-10mg of each sample was encapsulated in a hermetic aluminum sample pan.
You will need to use an analytical balance to find the mass of pure samples in the sample pans. Your
instructor will give you the mass of the empty pans. You do not need to do this for the mixed samples.
INSTRUMENT OPERATION:
Set-Up:
1) Turn power on to instrument and computer using power strip.
2) Turn on N2 purge gas and adjust to a flow of 50 mL/min.
3) Log on to computer using Login Name = ISBT Program, PW = isbt
4) Click on icon for Q10-0016 instrument within the Q Series Explorer window.
Experimental Run:
1) Install sample and reference pans on sample holder platform:
a) Using tweezers, remove sample covers.
b) Place empty aluminum sample pan as a reference at 11 oclock position on holder.
c) Place sample pan at the 4 oclock position on sample holder platform.
d) Use tweezers to replace sample cover and furnace cover.
2) Go to View / Experiment View
a) On Summary tab, enter following information
Mode = Standard
Test = Ramp
Sample Name
Sample Size (in mg)
Data File Name (click on the book icon to the right of Data File Name)
b) On Procedure tab
Test = Ramp
Start Temp = 60C, Heating Rate = 10C/min, Final Temp =150C
c) On Notes tab
Pan Type = Aluminum Hermetic
Purge Gas = Nitrogen at 50mL/min
3) When the temperature is below 60C then you can start the run (temp. shows at top of screen)
a) Hit Triangle icon at top left to start run will automatically stop when done.
b) Once you start the run then go to View/ Real Time Plot View to watch the results.
c) If you want to prematurely Stop then the Square icon will stop the run and store the data.
The Up arrow with Bar underneath will Reject the run and will discard the data.
4) If the lower-temperature peak shows as a significant doublet set of peaks, immediately Reject
the run and let the instrument cool back down to below 60C, then restart the run. The doublet
is due to hydrogen-bonding of the benzoic acid in solution to form dimers. The dimer doublet
will appear if the sample was previously cooled too rapidly to allow the liquid dimers to
dissociate to form the preferred monomeric solid crystal.
5) When done with the first run, you can remove the main insulating cover from the sample area to
speed the cooling, but leave the sample in place until it cools below 70C.
CAUTION: The metal parts of the instrument are HOT. Use tweezers to handle parts.
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