Binary Solid/Liquid Phase Diagrams

(Differential Scanning Calorimeter)

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)

where xsolute is the concentration of solute in units of mole

fraction, T*solvent is the melting temperature of the pure solvent,
and Hfus,solvent is the enthalpy of fusion for the pure solvent.

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

As a second option, we can consider the same

solution of benzoic acid and cinnamic acid, but at the
opposite end of the compositional range, i.e. almost
pure benzoic acid solvent (xB 1.0) with only a small
amount of cinnamic acid present. The same general
behavior is seen as with the previous scenario the
liquid phase is a mixture of solute and solvent and the
solid phase is pure solvent. The only difference on
the right and left sides is that the two compounds flipflop with each other with respect to which is the
solute and which is the solvent.

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:

-2-

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.

-3-

An alternative method of monitoring phase transitions is to do

the reverse measure the amount of heat needed to raise the
temperature at a constant rate. During the heating of a solid or
liquid the incremental heat (J/C) is the heat capacity of the
material. During a phase transition, however, a much larger
input of heat is needed (or released) to convert the material from
one phase to another. The integrated area of this peak should
equal the enthalpy of the transition. The location of the peak
defines the transition temperature.

phase
transition
d
oli
fs
o
ng
ati
he

ing
at
he

uid
liq
f
o

Time at Constant Heat Flux

(total amount heat added)

Incremental Heat (J/C)

One method of mapping phase transitions is to start with a solid

sample. The mixture is then heated with a constant rate of heat
flow while monitoring the temperature. This gives an initial
zone of heating due to the heat capacity of the solid. When a
phase transition is reached, the temperature remains constant
while the heat is used for the transition. Once the transition is
complete, the temperature resumes rising. While this method
works in principle, it is time consuming and is not very precise.

Temperature

DIFFERENTIAL SCANNING CALORIMETRY

phase
transition

heat capacity
of solid

heat capacity
of liquid

0
Temperature of Sample

A differential scanning calorimeter (DSC) can be used to

measure the 2nd of the curves above. It delivers a high level of accuracy by comparing the heat
necessary to raise the temperature of the sample to the heat necessary to raise the temperature of
a nearby reference sample. This differential comparison eliminates systemic errors that can
arise as the temperature of the instrument changes during an experimental run. A DSC differs
from a bomb calorimeter in that the former uses heat as a control parameter while in the latter
heat is an output parameter.
We will use a DSC-Q10 (TA Industries) for our work. It has a circular furnace block to which
are attached mounts for the sample cell and the reference cell. We will use an empty aluminum
pan as our reference (for which the instrument has already been calibrated versus a standard
indium sample). The instrument monitors the individual temperatures of the sample and
reference as the underlying furnace block is raised in temperature. It then compares and reports
the additional heat required to bring each of the individual cells to the same temperature.
Top View
(reduced in size)

Side View
Reference Cell

Sample Cell

reference
(empty pan)

reference cell

sample
aluminum pan

furnace block

cell mount

temperature
sensor
furnace block

sample cell

-4-

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.

-5-

To Analyze Data and to Export as .txt File:

1) Open TA Universal Analysis program
2) Click on File / Open to open the data file that you collected with the instrument
Will have chance to correct information if you need to, otherwise hit Ok
3) To export the open data to a .txt file
Go to File / Export Data File / File Signals Only
Hit Finish
Specify name of export file adding .txt file extension to the end of the name
Determining Transition Temperatures:
The typical approach to reporting the transition temperature of a pure material is to report the
onset temperature. This is the temperature at which the heat flow begins to increase. Because of
the difficulty present with overlapping points near the eutectic point we will need a different
strategy. We will use the peak temperature for each of the transitions that are visible on the
thermogram. If there is a doublet for the lower transition, then use the peak that is at the higher
temperature of the two.
The peak temperatures can be manually taken from the export file. Alternatively they can be
determined using the TA Universal Analysis software.
a) Open the data file using File / Open
b) Click on Analyze / Peak Max on the top menu
c) Left click on the red crosses and move to the beginning and the end of the peak.
d) Right click on an open area of the graph and select Accept Limits
e) Program will show the temperature corresponding to the maximum of the peak.
The area under the peak (as well as onset temperature and peak temperature) can also be found
using the TA Universal Analysis software. You will need to do this for the pure samples so that
you can determine the enthalpy of fusion.
a) Make sure you entered your newly measured masses for the pure samples.
b) Open the data file using File / Open
c) Click on Analyze / Integrate Peak / Linear on the top menu
d) Left click on the red crosses and move to the flat area right before and right after the
peak. The program will draw a line between the two and then integrate the area
under the peak.
e) Right click on an open area of the graph and select Accept Limits
f) The program will show the onset and the peak temperatures. It also will show the area
under the graph in units of J/g. This corresponds to the enthalpy of fusion for
the pure material after converting from grams to moles of material.
LAB REPORT
Your lab report should include a tabulation of the transition temperatures for each of the samples
that you measured. You should then transform those data into a graphical phase diagram
showing both phase transitions, labeling each phase region of the diagram. Your report should
also include representative thermograms from the different regions of the phase diagram
including at least one pure sample, a sample showing two peaks, and the sample taken at the
eutectic point.

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