Lab 13 Thermodynamics: Thermochromic Equilibria
Lab 13 Thermodynamics:
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CHEM 144 Quantitative Analysis II 2021-2022 First Edition
40 Lab 13 Thermodynamics: Thermochromic Equilibria 41
Thermochromic Equilibria
Lab 13 Table of Contents
Lab 13 Background................................................................... 43
13.0 Objective ............................................................................... 43
13.1 Cobalt Chloride Alcohol Equilibria .......................................... 43
13.2 Equilibrium Constant (!"). .................................................... 44
13.3 Writing the Cobalt Chloride Alcohol Equilibrium Constant
Expression in Terms of Experimentally Measurable Variables ........ 45
13.4 Dependence of !" on Temperature ....................................... 49
Restricting !" to 10 oC in a Van’t Hoff Analysis .......................................50
Finding ∆$, ∆% and ∆& (at various ") - Worked Example ........................50
Lab 13 Procedure ..................................................................... 51
Objectives .................................................................................................51
Equipment and Supplies ...........................................................................51
Prepare the CoCl2(iPrOH)3:MeOH Reaction Solution ................................52
Spectrophotometer and Surface Temperature Sensor Set-Up .................52
Calibration for Absorbance Measurements ..............................................53
Preparing Logger-Pro for Simultaneous Capture of Absorbance and
Temperature over a Defined Time Interval ..............................................53
Chilling the Reaction Mixture ...................................................................55
Running the Sample ..................................................................................55
Clean up ....................................................................................................58
Data Work-Up ...........................................................................................58
Preparation for Lab 13: A Student Guide
Important: You will need Logger Pro installed on your laptop to
communicate with, and collect data from, a vis-NIR spectrophotometer and
surface temperature sensor (STS) in lab. Logger Pro is a free download – see
the document on D2L. Lab 13 also depends heavily on EXCEL, so you will
want this program installed and working on your laptop as well.
Lab 13 seeks to characterize the equilibrium and thermodynamic behavior of a
chemical system. We will do this by finding the equilibrium constant (! at
different temperatures and use this data to determine two important
thermodynamic physical quantities for the system, enthalpy ∆) and entropy ∆*.
The sign of the enthalpy value (which follows from the behavior of (! with +),
reveals if the system is exothermic or endothermic. With ∆) and ∆* known, the
Gibbs free energy ∆, at specific + can be calculated to explore the equilibrium
directionality at different temperatures.
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Lab 13 Thermodynamics: Thermochromic Equilibria 42 Lab 13 Thermodynamics: Thermochromic Equilibria 43

Lab 13 Background
However, a more important feature of Lab 13 is the interplay of theory and
experiment – the application and building of mathematical models coupled to
what can be measured experimentally. This captures the flavor of modern
quantitative chemistry. As you will see, Lab 13 is built from theoretical models
13.0 Objective
and conceptual simplifications integrated with modern laboratory tools and
methods, and the extensive use of a computation resource (spreadsheet The central goal of Lab 13 is to characterize the thermodynamic behavior of a
program). Lab 18 embraces a very similar design but applied to kinetics. The chemical system. As a model system, we have selected one that changes color
overall approach of Labs 13 and 18 has relevance to how actual quantitative with temperature, that is, a chemical system that exhibits thermochromism. In
problems are handled and offers direct experience in carrying out such analyses. such systems, temperature changes induce shifts in the chemical equilibrium
(In a way Labs 13 and 18 are two “bookends”, one concerned with a between compounds with distinctly different colors. Since the compounds are
thermodynamic-equilibrium problem, the other a kinetic analysis.) colored, (light absorption in the visible spectrum), a vis-NIR spectrophotometer
Lab 13 runs for one session. The procedure on pages 51 - 59 presents the steps can be used to follow and quantitate the temperature driven change.
in detail.
To get started, first review sections 13.1 and 13.2 (pages 43 - 44) which are
13.1 Cobalt Chloride Alcohol Equilibria
compact sections that present some fundamentals. Section 13.3 (pages 45 - 48)
Some metal coordination complexes exhibit thermochromism. Such complexes
develops a key equation (13.7) behind the Lab 13 Spreadsheet you will use to
consist of a central metal atom or ion with a surrounding array of bound
calculate (! at 200 different temperature points! Manually performing such a
molecules or ions, known as ligands. The types and number of ligands affect the
calculation 200 times would certainly be impractical, so we are providing you
energy state of electrons in the coordination complex and thus determine the
with a prepared spreadsheet to handle the heavy lifting. To develop equation
system’s color.
(13.7) section 13.3 employs a tour de force in applied chemistry – that said, it
When cobalt (II) chloride (CoCl2) is dissolved in isopropanol (abbreviated iPrOH), Methanol
should prove accessible with an investment of some quality time. Fortunately,
it forms a metal coordination complex with the formula CoCl2(iPrOH)3 that (CH3OH)
you can successfully complete Lab 13 without knowledge of section 13.3 – that
(MeOH)
is, the details are presented for those interested, but you are not required to appears blue in color. When CoCl2(iPrOH)3 is combined with methanol
d = 0.792 g/mL
learn this material to perform well on the lab. (abbreviated MeOH) a chemical reaction occurs resulting in
M = 32.04 g/mol
Le Chatelier’s
CoCl2(iPrOH)2(MeOH)3, a metal coordination complex that appears pink to the
On the other hand, section 13.4 should be studied with care, for this section principle
describes how, eye:
addresses how to find ∆) and ∆* from the (! versus + data, and then ∆, at
when a dynamic
specific +. While the math in Lab 13 may seem involved, you should find the lab equilibrium is CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH (13.1)
rather doable and, in the end, perhaps even satisfying for having tackled such a disrupted by a
Blue Colorless Pink Colorless
change of
challenging experiment. pressure,
temperature, Note this is an equilibrium (signified by the ⇄). This suggests that one can control
Don’t forget to bring to lab:
volume or the color of CoCl2 alcohol solutions by shifting the equilibrium to favor products
concentration, the
• The CHEM 144 Lab Manual. or reactants. For example, introduction of additional MeOH into the system
position of
equilibrium will would by Le Chatelier's principle favor the products side, and thus the chemical Isopropanol
• A laptop computer with Logger Pro and EXCEL installed.
shift to counteract system would appear pinker due to the formation of more (CH3CHOHCH3)
• A digital copy of the EXCEL file Lab 13 Spreadsheet (on D2L). any change and (iPrOH)
CoCl2(iPrOH)2(MeOH)3.
restore an
d = 0.786 g/mL
• A digital copy or hardcopy (printout) of the Lab 13 Worksheet. equilibrium state.
The extent of this cobalt chloride alcohol reaction (13.1) also depends on the M = 60.10 g/mol
Additionally, you will need for lab: Hence, if we have: system temperature. To illustrate, assume the reaction is exothermic (generates
A + heat ⇄ B heat; heat on the product side as signified by the “Δ”),
• Your face covering, goggles, lab coat and gloves. and we add heat,
then more B is
• A Sharpie® fine point marker (or something similar). formed, or if the CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH + Δ
amount of B
• Loose-fitting, long pants and completely closed shoes. increases, A and In this case, increasing the temperature would favor formation of the reactant
heat must
CoCl2(iPrOH)3 and the chemical system should become more bluish as the
increase.
system shifts to the left from an increase in Δ on the right. Conversely, if the

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Lab 13 Thermodynamics: Thermochromic Equilibria 44 Lab 13 Thermodynamics: Thermochromic Equilibria 45

reaction was endothermic (requires heat; heat on the reactant side), 13.3 Writing the Cobalt Chloride Alcohol Equilibrium
Δ + CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH
Constant Expression in Terms of Experimentally
Measurable Variables
Then increasing the temperature would favor the product CoCl2(iPrOH)2(MeOH)3
and the system should appear pinker. Using (13.4) the value of (! can be determined if we know the equilibrium
concentrations of all species in the system. Unfortunately, it is very difficult to
measure the concentration of CoCl2(iPrOH)2(MeOH)3, iPrOH, CoCl2(iPrOH)3 and
13.2 Equilibrium Constant (!. ). MeOH directly – and using some ingenuity it turns out this is not necessary!
When studying chemical equilibria of solutions, a good starting point is to Let us begin by considering the reactant side of (13.1). Here we are reacting
determine the equilibrium constant ((! ). The subscript “C” refers to molar CoCl2(iPrOH)3 with MeOH. Assume we take a volume /" of CoCl2(iPrOH)3 solution
Concentration. To understand (! better, consider the generic balanced chemical with an initial molar concentration 0# (which is 0.0103 M for Lab 13). Given this,
equation: how would you symbolically express the moles of CoCl2(iPrOH)3 that you are
aA + bB ⇄ cC + dD starting with? Did you obtain /" 0# ? Remember, volume (L) times molar
(13.2)
concentration (mol/L) gives you moles. As an organizational aid, we prepare a table
Reactants Products in moles and label a row for the initial moles of each reactant and product:

In which the capital letters represent chemical formulas of the reactants and
products, and the lower-case letters are the stoichiometric coefficients (the CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH
numbers in front of the chemical formulas). As indicated, the reactants are on the
left, the products on the right. For this generic balanced chemical equation, the Initial Moles /" 0# ?
equilibrium constant expression is:
Why moles? You should be able to answer this question. Hint: think about the
[']" [)]#
$! = (13.3) balanced equation (13.1); is the balance in terms of mass, molar concentration,
[*]$ [+]%
molar mass, or moles? Remember, a balanced chemical equation only speaks in
moles – that is why in using the stoichiometric relationships of a balanced chemical
Here the brackets signify molar concentrations of the reactant or product enclosed
equation we must convert to moles.
by the bracket. From (13.3), we see that (! is the ratio of the product molar
concentrations raised to their stoichiometric coefficients over the reactant molar Now consider the other reactant, methanol. Initially we introduce a volume,
concentrations raised to their stoichiometric coefficients. So clearly, if the reactant /$%&' , of methanol. If you know the volume of a liquid such as MeOH, how would
molar concentrations are greater at equilibrium than the product molar you find the moles? Consider the solvent information given in the sidebar on page
concentrations, (13.3) predicts (! should be smaller than an equilibrium condition 43 for methanol. How can you combine the density, molar mass and /$%&' to
in which the product molar concentrations are greater than the reactant molar arrive at the moles of MeOH in /$%&' ? Did you obtain 1$%&' /$%&' /2$%&' ? If not,
concentrations. try to figure out why. Remember density (g/mL) times volume (mL) gives you mass
(g); mass (g) divided by molar mass (g/mol) gives you moles. These are
Applying the above to the cobalt chloride alcohol system of (13.1), results in:
fundamental manipulations – try to make them second nature. Let us enter this
into our table:
[','-& (/0123)& (5623)' ][/0123]
$! = (13.4)
[','-& (/0123)' ][5623]'
CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH

Examine (13.1). Assume the equilibrium strongly favors the product side. Would 1$%&' /$%&'
you expect (! to be large or small? From (13.1), if the equilibrium strongly favors Initial Moles /" 0#
2$%&'
the products, then [CoCl2(iPrOH)2(MeOH)3][iPrOH] > [CoCl2(iPrOH)3][MeOH]3, so
that (13.4) predicts a large (! ((! >> 1). Notice the reverse would be true if the
We next consider the product CoCl2(iPrOH)2(MeOH)3. Under initial conditions, that
equilibrium strongly favored the reactant side – namely (! would be small ((! <<
is before the reaction occurs, obviously no moles of CoCl2(iPrOH)2(MeOH)3 would
1). Hence, the magnitude of (! affords insight as to where the equilibrium lies.
be present, so:

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 Lab 13 Thermodynamics: Thermochromic Equilibria 46 Lab 13 Thermodynamics: Thermochromic Equilibria 47

CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH

CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH
1$%&' /$%&' 1()*&' /"
Initial Moles /" 0# 0
2$%&' 2()*&'
1$%&' /$%&'
Initial Moles /" 0# 0
2$%&'
Change in
−4 −34 +4 +4
Moles
Finally, we come to the moles of iPrOH. The initial moles of iPrOH cannot be “0”.
Why? The CoCl2(iPrOH)3 solution is prepared by dissolving CoCl2 in iPrOH, giving a Equilibrium 1$%&' /$%&' 1()*&' /"
/" 0# − 4 − 34 4 +4
CoCl2(iPrOH)3 solution with virtually no free CoCl2. The CoCl2(iPrOH)3 solution is in Moles 2$%&' 2()*&'
0.01 M range. So, using chemical intuition, what makes up the greater bulk of this
solution, CoCl2(iPrOH)3 or the iPrOH? Clearly, it must be iPrOH. In other words, the Again, note that we have used the densities (1) and molar masses (2) of the
moles of solvent, iPrOH, is vastly greater than the moles of CoCl2(iPrOH)3. different alcohols to estimate the corresponding number of moles (n = 1//2) from
Therefore, the initial moles of iPrOH cannot be “0.” We can calculate the initial a given volume (/) of those alcohols.
moles of iPrOH in a manner similar to that for MeOH; that is, we assume the
Now we make one more simplifying assumption, namely that 4 moles is very much
volume of initial solution /" is essentially just iPrOH, so using the density and molar
smaller than the moles of MeOH or iPrOH. This seems reasonable for the moles of
mass (as we did for MeOH), we arrive at 1()*&' /" /2()*&' . Hence, we have:
4 are limited to the 0.01 M range, while the moles of MeOH or iPrOH are orders of
magnitude greater. Applying this assumption gives at equilibrium:
CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH

1$%&' /$%&' 1()*&' /"

CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH
Initial Moles /" 0# 0
2$%&' 2()*&'
Equilibrium 1$%&' /$%&' 1()*&' /"
/" 0# − 4 4
Moles 2$%&' 2()*&'
When mixed, some of the CoCl2(iPrOH)3 will react with the methanol to form
CoCl2(iPrOH)2(MeOH)3. We don’t know how much, so let us call 4 the number of
Here we have eliminated the rows corresponding to the initial moles and change
moles of CoCl2(iPrOH)3 that react. Now think. For every 4 moles of CoCl2(iPrOH)3
in moles, for they have served their purpose in developing the equilibrium terms
that react the stoichiometry of the balanced chemical reaction (13.1) demands 34
and we are focusing on just the equilibrium.
moles of MeOH are consumed and 4 moles of CoCl2(iPrOH)2(MeOH)3 are formed
along with 4 moles of iPrOH. Since we can experimentally determine the concentration of CoCl2(iPrOH)3 at
equilibrium using spectrophotometry, the value of 4 can be determined. How? If
Because this represents a change in moles from the initial condition, we create a
we measure the absorbance of CoCl2(iPrOH)3 at equilibrium, we can find the
second row in our table to represent the change based on “4”. Note the signs! On
concentration via the Beer-Lambert law. (Using the approach of Lab 6 from CHEM
the left, CoCl2(iPrOH)3 and MeOH are consumed, hence the (-) sign; on the right,
143, it has experimentally been found that CoCl2(iPrOH)3 has a 8+,- at 656 nm
CoCl2(iPrOH)2(MeOH)3 and iPrOH are formed, and so (+). Be certain you
with a molar absorptivity 9./. of 319 cm-1M-1.) Let’s call this concentration of
understand this; without the correct signs, the mathematics will not work out.
CoCl2(iPrOH)3 at equilibrium 0%0 . Now clearly, if we multiply by the total volume of
the reaction mixture, /123 = /" + /$%&' , then we will have the moles of
CoCl2(iPrOH)3 + 3 MeOH ⇄ CoCl2(iPrOH)2(MeOH)3 + iPrOH CoCl2(iPrOH)3 at equilibrium, which according to our table is /" 0# − 4. Hence, we
have:
1$%&' /$%&' 1()*&' /" 0%0 /123 = /" 0# − 4 (13.5)
Initial Moles /" 0# 0
2$%&' 2()*&'
Solving the Beer-Lambert law (;./. = 9./. <0%0 ) for 0%0 and substituting into
Change in (13.5) gives,
−4 −34 +4 +4
Moles ;./.
= > / = /" 0# − 4
9./. < 123
Finally, we can write the moles (NOT CONCENTRATION) at equilibrium for each of
the chemical species by “adding” down the columns: Recall, the immediate objective is to find 4. Solving for 4 results in,

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Lab 13 Thermodynamics: Thermochromic Equilibria 48 Lab 13 Thermodynamics: Thermochromic Equilibria 49

;./. In the Lab 13 procedure you are chilling a CoCl2(iPrOH)3 + MeOH reaction solution,
4 = /" 0# − = >/
9./. < 123 then transferring the chilled solution into a cuvette. Subsequently, the loaded
cuvette is placed in a spectrophotometer with a special temperature probe added
This is an important result, for you have 4 in terms of values known or
to measure the solution temperature while in the cuvette. As the cuvette sits in
measurable in the lab. Once 4 is known, all the equilibrium concentrations can be
the spectrophotometer, the solution warms. Collecting ;./. and + measurements
determined by dividing the number of moles of each species by the total volume
for 200 seconds every second results in two hundred ;./. versus + data pairs.
(/123 ) of the mixture. In other words, we will have:
Applying the Lab 13 Spreadsheet to this ;./. versus + data, then provides the (!
3 versus + data required to find ∆) and ∆*. This means in a mere 200 seconds all
/# "$ − /# "$ + 24 %&%56 /'() 3%&% the raw data needed to complete the analysis is captured! Without (13.7) and the
%&%
["#"$! (&'()*)" ] = . 7=
/'() 4%&% 5 spreadsheet, the experiment becomes more complicated, and certainly will
require far more than 200 seconds to capture all the raw data.
:*+,- /*+,-
[89)*] =
8*+,- /'() 13.4 Dependence of !. on Temperature
3
/# "$ − 24 %&%56 /'() /# "$ 3%&% The equilibrium constant ((! ) should be independent of the initial concentration
%&%
["#"$! (&'()*)! (89)*)" ] = . 7= −
/'() /'() 4%&% 5 of the different species. However, the temperature of the system can
affect (! .The Van’t Hoff equation states a relationship between (! and + in
:./0,- /# Kelvins:
[&'()*] =
8./0,- /'() ∆) 1 ∆*
ln((! ) = − + (13.8)
C + C
Substituting the above equations into (13.4) will then give you (! for any given
volume ratio of CoCl2(iPrOH)3 (/" ) to MeOH (/$%&' ). Can you carry this out? That
E = F ∙ 4 + <
is, can you write (13.4) strictly in terms of values known or measured? This is an
important connection between the theoretical (13.4) and the experimental (what where ∆) and ∆* are the enthalpy and entropy change of the reaction,
we can measure in the lab). Once these measured values are in hand, determining respectively, and C is the ideal gas constant (C = 8.314 J/(K·mol)). This
the equilibrium constant (! should be straightforward using the revised equation. relationship suggests that the value of ∆) and ∆* may be derived experimentally
using (! values at different temperatures, + (in Kelvin). This can be accomplished
Here is the result for the above substitutions into (13.4), by plotting ln((! ) versus 1/ + to prepare a Van’t Hoff plot which should result in
a straight line with slope, F = −∆)/C and E-intercept, < = ∆* /C.
/" 3 : /
2 /# $ − 4 %&%56 28 ./0,-/ # 6
;1 = '() %&% ./0,- '()
(13.6) Enthalpy change and entropy change are signed values.
3 :*+,- /*+,- "
24 %&%56 2 8 / 6
%&% *+,- '() ∆) < 0 → exothermic processes

Plugging in the known values for 0# , 9./. , <, 1()*&' , 2()*&' , 1$%&' , and 2$%&' ∆) > 0 → endothermic processes
gives: ∆* < 0 → decrease in “disorder” (for an isolated system)
I
0.0103 8 ∙ /# 3%&% 0.786 JK ∙ /# ∆* > 0 → increase in “disorder”
< / +/ − D
319 82# E60.10 I (/ + / L
*+,- )
# *+,-
J#$ # ∆), ∆* and + (in Kelvin) are related to Gibbs free energy change, ∆,, by:
;1 = " (13.7)
I
3%&% 0.792 JK ∙ /*+,-
< DE L
319 82# 32.04 I (/# + /*+,- ) ∆, = ∆) − +∆* (13.9)
J#$
Hence, with the enthalpy and entropy change of the reaction system known,
(13.7) is the equation behind the Lab 13 Spreadsheet. But exactly why is this so
evaluation of Gibbs free energy change can follow. In general:
important? Because /" and /$%&' are constant (fixed) for a given trial, hence by
using (13.7) only the absorbance of one chemical species (CoCl2(iPrOH)3 at 656 nm)
∆, < 0 → (! > 1 → directionality is product favored
needs to be measured and from that one value, (! can be calculated!
∆, = 0 → (! = 1
This makes possible the vast experimental simplification employed in Lab 13.
∆, > 0 → (! < 1 → directionality is reactant favored

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Lab 13 Thermodynamics: Thermochromic Equilibria 50 Lab 13 Thermodynamics: Thermochromic Equilibria 51

Restricting "# to 10 oC in a Van’t Hoff Analysis Hence, for example system of Graph 13-1, ∆* = −256 UR⁄J#$ implies an
exothermic process, and ∆V = −926 R⁄; ∙ J#$ suggests a decrease in “disorder.”
One important point remains unaddressed. Examine equation (13.8). Does
Now suppose we wish to find ∆, at 1.0 °C and 5.0 °C.
something seem odd? Notice in this equation the enthalpy and entropy change
are NOT functions of temperature – as written both are constants. In (13.8) only At 1.0 °C:
(! varies with temperature. Does this sound correct? ∆X = ∆* − Y∆V
UR R UR
Fundamentally, ∆) and ∆* are both functions of temperature – that is, they vary ∆X = 2−256 6 − (274.15 ;) 2−926 62 6
J#$ ; ∙ J#$ 10" R
with temperature. This means for (13.8) to hold, the temperature range must be
UR
restricted such that ∆) and ∆* remain, for all practical purposes, constant. In ∆X = −2.1
J#$
practice, if H+ (lowest to highest temperature in the analysis) remains within a
At 5.0 °C:
10 °C range, application of (13.8) is justified (∆) and ∆* should behave as
∆X = ∆* − Y∆V
temperature independent quantities). You will note in the Lab 13 work up
UR R UR
section (page 59) the instructions specify restricting H+ to 10 degrees Celsius. ∆X = 2−256 6 − (278.15 ;) 2−926 62 6
J#$ ; ∙ J#$ 10" R
Now you can appreciate why this must be done when applying (13.8) to
UR
determine ∆) and ∆* for the system. ∆X = 1.6
J#$

Finding ∆%, ∆& and ∆' (at various #) - Worked Example
To illustrate finding ∆), ∆* and ∆, (at various +), let us consider a system for
which a set of (! versus + values result in the following ln((! ) versus 1/ + plot
(remember, temperature + must be in Kelvins).
Thus, at 1.0 °C (274 K), the above system is product favored. However, at 5.0 °C,
with DGrxn = +1.6 kJ/mol, the system clearly reverses directionality, being
reactant favored.

Graph 13-1. ln(Kc) vs. 1/T Lab 13 Procedure

2.00

1.00
Objectives
0.00
0.00346 0.00348 0.00350 0.00352 0.00354 0.00356 0.00358 0.00360 0.00362 0.00364 0.00366 Overall objective: infer the values of ∆) and ∆* for a chemical reaction involving
-1.00
ln(Kc)

CoCl2(iPrOH)3 with MeOH and analyze the thermodynamic behavior.

-2.00

-3.00 y = 30809x - 111.39 In particular:

-4.00
R² = 0.9998 • Prepare a 2.5:1.5 CoCl2(iPrOH)3 : MeOH volume ratio, chill and capture
-5.00 ;./. and + concurrently. From this raw data, determine (! as a function
1/T (K-1) of temperature + using the EXCEL file Lab 13 Spreadsheet.

• From the EXCEL spreadsheet output, work-up the (! versus + data to

From the slope (m) of the trend-line we find:
determine ∆) and ∆*. (Hint: this will involve constructing a Van’t Hoff
∆* plot, and the temperatures must be in Kelvin). Assess exothermic vs.
J=− ⟹ ∆* = −JP
P endothermic and irreversibility/disorder.
R R UR
∆* = −(30809 ;) 28.314 6 = −2.56 × 10& = −256 • Calculate ∆, at specific temperatures. Assess directionality and extent.
; ∙ J#$ J#$ J#$

And from the y-intercept (b) of the trend-line we have: Equipment and Supplies
∆V
5=
⟹ ∆V = 5P
P Expendables
R R a) Plastic transfer pipettes (in boxes on the islands)
∆V = (−111.4) 28.314 6 = −926
; ∙ J#$ ; ∙ J#$ b) 3x 20 mL Plastic vial and cap (in a bin on the reagent bench)
c) 1x 2-dram (7 mL) glass vial and cap (in a bin on the reagent bench)

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Lab 13 Thermodynamics: Thermochromic Equilibria 52 Lab 13 Thermodynamics: Thermochromic Equilibria 53

d) 3x Standard-size cuvettes without caps (Styrofoam™ boxes on the

DO NOT cap the
islands) cuvettes in Lab Fit is loose by
e) Kimwipes™ (dispenser attached to the islands) 13. With design.
isopropanol in the
Chemicals cuvette, the
pressure applied Lead wires.
f) 10 mL of 0.0103 M CoCl2(iPrOH)3 stock solution - use a 20 mL vial & cap Surface temperature
by a tight-fitting
to control evaporation and spills; DO NOT USE A BEAKER! cap will cause the sensor body.
g) 10 mL of Methanol - use a 20 mL vial and cap to control evaporation polystyrene Cuvette.
and spills; DO NOT USE A BEAKER! cuvette to split! USB
Isopropanol (and
h) ≈ 5 - 10 mL of Isopropanol - only for zeroing the spectrophotometer - methanol) Sensor tip.
use a 20 mL vial and cap; DO NOT USE A BEAKER! mechanically
i) Ice Melter (depresses the melting point of ice, jars on the islands) weakens the
polystyrene
Equipment cuvette.

j) 20 - 200 µL micropipette + 200 µL tips (on the micropipette station) • Align the sensor so the tip is not touching the cuvette interior and is
k) 100 - 1000 µL micropipette + 1000 µL tips (on the micropipette positioned several millimeters above the cuvette bottom. The lead wires
station) must be in one corner of the cuvette to avoid obstructing the optical path.
l) Vis-NIR Spectrophotometer + USB cable (attached to the islands) With the greatest care, you may adjust the alignment of the sensor tip and
m) Vernier surface temperature sensor (STS) with Go!Link interface lead wires but avoid bending the wires any more than necessary.
(digital temperature probe for measuring the temperature of a
solution in a cuvette) • Launch Logger Pro. If the spectrophotometer and temperature sensor are
n) Plastic ice bowls (on the reagent bench, only 1 per student; the ice communicating properly, the absorbance and temperature windows (both
machine is located in the hallway) in the lower left corner) will display readings.
o) Contents of bench equipment bin (see inventory sheet on page iii)
Calibration for Absorbance Measurements
Prepare the CoCl2(iPrOH)3:MeOH Reaction Solution DO NOT cap the
• From the Experiments menu select: Calibrate>Spectrometer:1. cuvettes in Lab
13. With
Using a clean, dry 2-dram (7 mL) screw cap glass vial, combine 2.50 mL (2500 µL) The surface • The Calibrate Spectrometer dialogue box will open. isopropanol in the
of 0.0103 M CoCl2(iPrOH)3 and 1.50 mL (1500 µL) of methanol. Keep vial capped. temperature cuvette, the
sensor (STS) must a. If spectrophotometer has been OFF, wait 90 seconds for warm-up. pressure applied
remain stored on b. If spectrophotometer has been ON for at least 90 seconds, click Skip by a tight-fitting
Spectrophotometer and Surface Temperature Sensor Set-Up its custom-made cap will cause the
Warmup and go directly to the next step below.
bracket. Removal polystyrene
• Connect the spectrophotometer USB cable (cable with green tape) to one of the STS from
• Place “blank” cuvette (standard cuvette with pure isopropanol) in holder cuvette to split!
said bracket (Isopropanol
USB port of your laptop. (be certain you have the correct orientation) and click on Finish mechanically
should only be for

• The surface temperature sensor (STS) consists of a low thermal mass cleaning and Calibration. weakens the
alignment, or polystyrene
temperature sensor supported by a sensor body. A Go!Link interface is when running a • Next, click OK to close. cuvette.)
required to communicate with Logger Pro on your laptop. The Go!Link sample, in which
case it will be in
interface terminates in a USB plug (cable with blue tape). Connect this plug Preparing Logger-Pro for Simultaneous Capture of Absorbance
position on a
to a second USB port on your laptop. If you lack a second USB port, USB cuvette. Please do and Temperature over a Defined Time Interval
hubs (splitters) are available via checkout (orange slip) from the ILSG quad. not place the STS
on the bench
• Check the sensor tip alignment using a clean standard cuvette. The sensor (contamination) • Click on the Configure Spectrometer (rainbow) icon in the tool bar.
or allow it to
IS VERY FRAGILE! Exercise great care when handling. Carefully slip a clean • The Configure Spectrometer:1 Data Collection window will open.
dangle (which
cuvette over the sensor tip. The cuvette should loosely meet with the sensor damages the
• Under Collection Mode (on the left) the default is Absorbance vs Time. If
body as illustrated on page 53. leads)
the collection mode is set otherwise, select Absorbance vs Time.

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 Lab 13 Thermodynamics: Thermochromic Equilibria 54 Lab 13 Thermodynamics: Thermochromic Equilibria 55

• Next, select (by clicking the appropriate check box) the wavelength (λ max) Chilling the Reaction Mixture
for the absorbance readings. Do not change the other values. Click OK.
• Set up the ice bath. Obtain roughly 25 g of Ice Melter (which is calcium and
magnesium acetate with a dye). This amount of Ice Melter fills a 50 mL
1. Check to beaker between the 30 to 40 mL markings. Do not weigh out the Ice Melter,
ensure setting is as this is unnecessary, wastes time, and creates a mess that may be
Absorbance vs 2. Set wavelength to 656 harmful to the balances.
Time. nm by clicking check box.
• To a bowl of ice, introduce and work-in 25 g of Ice Melter. Use a plastic
stirring rod (bench equipment bin). What you are doing here is depressing
the freezing point of ice, so the ice bath reaches – 8 °C. (A plastic stirring
rod is preferred, as some metal spatulas will corrode over time.)

• Reaction solution should be in 2-dram (7 mL) glass vial. NOTE: Vial cap must
3. Click OK. be securely on, as water, salt and dye from the bath can significantly alter
the results. Add the capped vial to the ice bath.
• Click on the Data Collection (clock and graph) icon in the tool bar.
• A 4 mL reaction solution volume typically reaches – 8 °C in 5 to 10 minutes
with intermittent repositioning and in-situ spinning of the vial.
Click Data
Collection icon.
Running the Sample
.
• You are going to load cold sample into a standard cuvette, insert the loaded
• The Data Collection window will open. Mode should be Time Based.
cuvette into the spectrophotometer sample holder, place the surface
Collection Length default is 200 seconds. In most cases, this is a good
temperature sensor in position and then start the temperature and
starting point. Remember, you can always change the length for subsequent
absorbance data collection. You want to perform this with minimum
runs via this window. Be sure the time units are seconds (not minutes,
hesitation, as once removed from ice, the sample will rapidly warm.
hours, etc.). Set Sample Rate at 1 sample/second, 1 second/sample.
Organization is very important.
Activate Sample at Time Zero check box. Finally, click Done.
• The surface temperature sensor (STS) must remain stored on its custom-
made bracket. Removal of the STS from said bracket should only be for
1. Set Mode to 5. Activate Sample cleaning/alignment and when running a sample, in which case it will be in
Time Based. at Time Zero check
position on a cuvette. That’s it. Please do not place the STS on the bench
box.
(contamination) or allow it to dangle (which damages the leads).
Remember; perform the next step(s) with a minimum of hesitation, as once
2. For Length type removed from ice, the sample will rapidly warm.
in “200”.
• Transfer the reaction solution between vial and cuvette using a transfer
pipette to avoid water and Ice Melter contamination. Do not pour from the
3. Set time units to
vial into the cuvette. Micropipettes are not a good idea, as you cannot
seconds.
transfer the required 3 mL at once. To efficiently transfer ≈ 3 mL of chilled
reaction solution in essentially one smooth controlled operation try the
4. For Sample following:
Rate: type in “1”. 6. Click Done. a. With the transfer pipette tip away from the reaction solution, fully
squeeze the bulb. This maneuver avoids bubbling warm air into the
chilled solution and will draw 3 mL into the pipette upon releasing
the bulb.

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Lab 13 Thermodynamics: Thermochromic Equilibria 56
b. Insert tip to the very bottom of the chilled reaction solution and
draw up. The pipette’s tip must be at a slight angle to avoid
occluding the solution inflow.
c. Pick up and hold the cuvette by the translucent sides (NOT the
transparent sides that form part of the optical path). Now position
the pipette tip against one corner of the cuvette and dispense by
squeezing the bulb. The idea here is to avoid spills and soiling that
necessitates cleaning up. Never exceed ¾ full! Overfilling will
damage the spectrophotometer and STS!
d. Wipe cuvette exterior with Kimwipe™. Immediately place cuvette
in the spectrophotometer cuvette holder.
e. Quickly orient the surface temperature sensor (STS) into position.
Note: the STS loosely fits on the cuvette – this design is delibrate to
avoid seepage of the cobalt-alcohol solutions out of the cuvette as
they warm.
• Watch the Logger Pro temperature display. You will see the temperature fall
as the sensor cools. Initiate data collection when the temperature appears
to hit a minimum by clicking Collect (green rectangle with ►).
Click Collect.
Because of reaction solution warming in the transfer process and the heat
introduced by the cuvette and sensor (which were at room temperature
after all), your initial temperature will likely fall in the 7 - 10 °C range. This is
perfectly fine.
Ambient heat and heat from the spectrophotometer light source will slowly
raise the reaction mixture temperature over time, thus allowing you to
capture absorbance ;./. and temperature + pairs over a temperature range
of at least 10 degrees - which is the practical limit for characterizing this
system via (13.8).
• Data capture will automatically terminate at the end of the collection length.
Be certain you are saving the data!
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Lab 13 Thermodynamics: Thermochromic Equilibria 57
A Possible Technical Complication You May Experience and
How to Resolve It
When concurrently collecting ; and + values in Logger Pro, if you
encounter an apparent lag in the absorbance values – meaning some of
the recorded + values lack an associated absorbance, the problem is
likely the laptop. There is much more number crunching associated with
the spectrophotometer data flow than that of the STS. With an interval
as short as one second, the laptop may not be able to handle all the
processing the spectrophotometer data flow demands, and so typically
the spreadsheet will have a continuous + record, but the ; record has
gaps. The captured values are still usable; but you will have to delete all
the + values without ; values to clean up the data set.
Fortunately, you can try a simple fix. The strategy is to decrease the
number of samples averaged for each absorbance value displayed from
10 to 1.
So, on the far left of the menu bar, click on Absorbance…. The
Spectrometer 1 dialogue box will open. Set Sample to Average to “1”.
Leave everything else alone. Click the red “X” to close and update the
settings. This should eliminate the lag in absorbance values.
• Should a second run of the same solution be in order, transfer the solution
back to its original vial and repeat the Chilling Samples and Running a
Sample steps above.
• Clean the surface temperature sensor at the end of your run (or multiple
runs if testing the same solution repeatedly).
a. Obtain a small amount of pure solvent (isopropanol - 5 mL is
enough)
b. Hold the sensor by the body over a catch (waste) beaker with the
tip pointing slightly down (to keep the solvent from running into
the body). See photo below.
c. Using a transfer pipette gently rinse the sensor tip and lead wires.
Three rinses are usually sufficient.
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Lab 13 Thermodynamics: Thermochromic Equilibria 58 Lab 13 Thermodynamics: Thermochromic Equilibria 59

To apply the Van’t Hoff equation,

Be certain you have saved the raw data!
∆) 1 ∆*
ln((! ) = − +
Clean up C + C (13.8)

• Remove cuvette from the spectrophotometer.
• Using a transfer pipette gently rinse the surface temperature sensor tip and
lead wires as specified above. Three rinses are usually sufficient.
• Dispose of all solutions from the vials, cuvettes, beakers, and so forth, in the
liquid waste bucket (located in the waste hood).
you must keep H+ in your analysis (for ∆) and ∆*) within 10 degrees – this
means truncating your (! vs. + data set so that the lowest to highest
temperature in the analysis spans only 10 degrees. You will find the later (higher
temperature data) behaves more consistently. Hence, for example, you might
select the (! vs. + data from 15 - 25 C
̊ . This is only a suggestion – ultimately you
need to decide the best cut-off based on your data.

• Used transfer pipette(s) should be discarded in the Transfer Pipette Disposal
Jar on the bench or in the hoods.
• Without cleaning/rinsing, discard the used cuvettes and 20 mL plastic vials
(and caps) in the regular trash.
From the selected spreadsheet results build a ln((! ) vs. 1/ + graph in EXCEL and
infer values for ∆) and ∆*. You may find the worked example on pages 50 - 51
helpful. Take care with the units.
With ∆) and ∆* known, calculate Gibbs free energy (∆,) at 1.0 C
̊ using

• Without cleaning/rinsing, discard the used 2-dram vial (and cap) in the glass
waste box. ∆, = ∆) − +∆* (13.9)

• Dump the contents of the Ice bath in the sink with plenty of tap water Repeat the calculation for 20 C
̊ and 40 C
̊ . You may find the worked example on
running. Rinse the ice bath three times with water and return to the reagent
page 51 helpful. Show all work.
bench. Please DO NOT leave ice baths out for others to clean up.
In the Lab 13 Worksheet, analyze the results in complete sentences. What does
• Rinse all glassware (beakers) and plastic ware (plastic stirring rod) five times the sign of ∆) indicate? What does the sign of ∆* suggest? What do the
with D.I. water and allow dry over a paper towel. Return to the bench calculated ∆, results indicate about the directionality (product vs. reactant) and
equipment bin from where the items came. extent at 40 C
̊ versus 20 C̊ versus 1.0 C
̊ ?
• All labeling tape, used or unused, should go in the regular trash. Please do
not leave tape stuck to the islands and benches!

Please do not leave cuvettes in the

spectrophotometers!

Avoid leaving the surface temperature sensor

(STS) in place on a cuvette filled with cobalt-
alcohol solution longer than necessary.

Data Work-Up

Migrate the Logger Pro raw data into the Lab 13 Spreadsheet EXCEL file to
transform the absorbance measurements (;./. ) into (! values. This
spreadsheet is literally carrying out (13.7) for every absorbance value, saving you
considerable effort!

CHEM 144 Quantitative Analysis II 2021-2022 First Edition CHEM 144 Quantitative Analysis II 2021-2022 First Edition