International Journal of Thermophysics (2019) 40:71

https://doi.org/10.1007/s10765-019-2540-2

Physical Properties
of 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (mTBD)

Zachariah Steven Baird, et al. [full author details at the end of the article]

Received: 28 February 2019 / Accepted: 3 July 2019 / Published online: 12 July 2019
© The Author(s) 2019

Abstract
7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (mTBD) has useful catalytic properties
and can form an ionic liquid when mixed with an acid. Despite its potential useful-
ness, no data on its thermodynamic and transport properties are currently available
in the literature. Here we present the first reliable public data on the liquid vapor
pressure (temperature from 318.23 K to 451.2 K and pressure from 11.1 Pa to
10 000 Pa), liquid compressed density (293.15 K to 473.15 K and 0.092 MPa to
15.788 MPa), liquid isobaric heat capacity (312.48 K to 391.50 K), melting proper-
ties, liquid thermal conductivity (299.0 K to 372.9 K), liquid refractive index (293.15 K
to 343.15 K), liquid viscosity (290.79 K to 363.00 K), liquid–vapor enthalpy of vapor-
ization (318.23 K to 451.2 K), liquid thermal expansion coefficient (293.15 K to
473.15 K), and liquid isothermal compressibility of mTBD (293.15 K to 473.15).
The properties of mTBD were compared with those of other relevant compounds,
including 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-
ene (DBU), and 1,1,3,3-tetramethylguanidine (TMG). We used the PC-SAFT equation
of state to model the thermodynamic properties of mTBD, DBN, DBU, and TMG.
The PC-SAFT parameters were optimized using experimental data.

Keywords Density · mTBD · PC-SAFT · Thermodynamic properties ·

Vapor pressure

1 Introduction

7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (mTBD) has a variety of interesting

properties. For years it has attracted attention as a catalyst [1–4], and more recently

Electronic supplementary material The online version of this article (https://doi.org/10.1007/s10765-

019-2540-2) contains supplementary material, which is available to authorized users.

B Petri Uusi-Kyyny
[email protected]
Extended author information available on the last page of the article

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it has been studied for possible use in CO2 capture [5, 6]. It can also form an ionic
liquid when mixed with an acid, and some of these ionic liquids are able to dissolve
cellulose [7]. This ability to dissolve cellulose is the basis for the IONCELL-F pro-
cess, which produces textile fibers from woody biomass by using ionic liquids like
7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium acetate as a solvent [8, 9].
Although mTBD has properties that make it an industrially important chemical, no
data about its thermodynamic properties can be found in the literature. Additionally,
mTBD is one of a family of guanidine superbases [3] and information about it could
also be useful in understanding these superbases in general. The only values publicly
available are a density and a single vapor pressure value given on some safety data
sheets, and their accuracy is questionable, largely because the vapor pressure units
differ depending on the safety data sheet.
To address this gap, we have measured the liquid vapor pressure using two exper-
imental methods (temperature from 318.23 K to 451.2 K and pressure from 11.1 Pa
to 10 000 Pa), compressed liquid density (293.15 K to 473.15 K and 0.092 MPa to
15.788 MPa), liquid isobaric heat capacity (312.48 K to 391.50 K, 0.36 MPa), melting
properties, liquid thermal conductivity (299.0 K to 372.9 K), liquid refractive index
(293.15 K to 343.15 K), and liquid viscosity (290.79 K to 363.00 K) of mTBD. The
heat of vaporization (liquid–vapor), liquid thermal expansion coefficient, and liquid
isothermal compressibility were also calculated from the experimental data. The ther-
modynamic properties of mTBD were then modeled using the PC-SAFT equation of
state [10]. The measurement were made at atmospheric pressure (0.1 MPa), if not
specified otherwise.

2 Methods

2.1 Preparation and Purity of the mTBD

Three different samples of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (CAS num-

ber: 84030-20-6, structure in Fig. 1) were used. The first was prepared at the University
of Helsinki. The second was purchased from BOC Sciences (Shirley, NY, USA). The
third was a portion of the second sample that was distilled to further purify it (see
Sect. 2.6) (Table 1).

Fig. 1 Structure of
7-methyl-1,5,7-
triazabicyclo[4.4.0]dec-5-ene

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Table 1 Information about the 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene samples used in this work

Sample number Source Purification Water content (wt%) Purity (wt%)

1 University of Helsinki None 0.03 > 99.5

2 BOC Sciences None 0.04 97.2 ± 1
3 BOC Sciences Distillation 0.01 98.3 ± 1.7

The purity of the mTBD samples was analyzed using capillary electrophoresis
(CE). Experiments were carried out with an Agilent 7100 CE system from Agilent
Technologies (Santa Clara, CA, USA) equipped with a diode-array detector (detection
at 200 nm, 214 nm, and 238 nm) and an air-cooling device for the capillary cassette.
Uncoated fused silica capillaries were from Polymicro Technologies (Phoenix, AZ,
USA). Dimensions were 50 μm internal diameter and 375 μm outer diameter. The
length of the capillary up to the detector was 0.300 m, and the total length was 0.385 m.
A Mettler Toledo pH meter (Columbus, Ohio, USA) was used to adjust the pH of the
electrolyte solutions.
The capillary was coated with polybrene. Prior to the coating, the bare fused silica
capillary was pretreated by flushing it for 10 min with 1 M NaOH, followed by rinsing
with water for 10 min at a pressure of 94 000 Pa. To diminish the adsorption of
positively charged mTBD on the negatively charged fused silica capillary wall, the
capillary was flushed for 22 min with a 1 w/w% of polybrene solution [11]. Further, a
voltage of 3 kV was applied for 20 min with both capillary ends immersed in the vials
with the coating solution. To remove unreacted polybrene molecules, the capillary
was rinsed for 10 min with water and sodium acetate buffer solution (pH 4; ionic
strength of 25 mM), respectively. In order to regenerate the coating surface, a fast
3-step recoating of the capillary was performed after every eight CE run. This was
done by firstly flushing the capillary for 1 min with the coating solution, then keeping
the system steady state for 1 min (waiting step), and finally flushing the capillary with
water for 1 min.
The polybrene-coated capillary was characterized by checking the electro-osmotic
flow. Thiourea at a concentration of 0.5 mM dissolved in a sodium acetate buffer (pH
4; ionic strength of 20 mM) was used as a neutral electro-osmotic flow marker in all
measurements. A set of mTBD solutions at a concentration range of 0.01 mg·mL−1
to 0.2 mg·mL−1 was used to prepare the mTBD calibration curve. A negative voltage
of 25 kV was applied across the capillary. All samples were introduced at 1000 Pa
for 10 s. Before each run, the capillary was rinsed for 2 min with a sodium acetate
buffer (pH 4; ionic strength of 25 mM). The electrophoretic runs were repeated at
least 5 times. All results were evaluated with the ChemStation software purchased
from Agilent Technologies (Santa Clara, CA, USA).
The water content of the mTBD was determined using Karl Fischer titration. A
DL38 Karl Fischer Titrator (Mettler Toledo) was used along with the Hydranal Com-
posite 5 K titrant and the Hydranal Medium K solvent solution (both from Fluka
Analytical).

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The first sample had a purity greater than 99.5 wt%. The second sample had a
purity of 97.2 ± 1 wt% and contained 1.6 ± 0.1 wt% of the non-methylated 1,5,7-
triazabicyclo[4.4.0]dec-5-ene as an impurity. The third sample had a purity of
98.3 ± 1.7 wt%. Trace amounts of TBD were still detected in the first and third sam-
ples, but the amount was below the limit of quantitation, which was 0.0025 mg·mL−1 .
The electropherograms are presented in the Electronic Supplementary Material. Pure
mTBD is a colorless liquid at room temperature, and the first and third samples were
initially colorless. However, it was noticed that over time the mTBD sample took on
a yellow color. Even small amounts of an impurity can cause a color change. To see if
the purity had significantly changed, the first sample was reanalyzed when the yellow
color was noticed, but no impurities were detected. The yellow color may have come
from small amounts of oxidation products, which have been observed for a similar
base: DBN [12]. The second sample was yellow when obtained. The first sample was
used for most of the measurements. Only the heat capacity measurements and second
and third set of viscosity measurements were performed with the second sample. The
third sample was only used for some of the vapor pressure measurements.
mTBD is hygroscopic and can also react with CO2 in the air, so to minimize the
absorption of these compounds the mTBD was stored in closed containers. When it
was necessary to get some of the mTBD, the containers were opened only briefly.
In addition to mTBD, several different chemicals were used in running, calibrating,
or checking the devices used in this study, and a full list of these chemicals and their
suppliers can be found from the Electronic Supplementary Material accompanying
this article.

2.2 Liquid Compressed Density

Compressed densities of mTBD were measured using a DMA HP density meter

(Anton Paar, Graz, Austria). The pressure in the density meter was measured using
a UNIK 5000 pressure sensor (GE, Boston, MA, USA). For calibrating this pressure
sensor, a MC2-PE calibrator with an EXT600 external pressure module was used
(Beamex, Pietarsaari, Finland), and these had been calibrated by Beamex. The stan-
dard uncertainty of the pressure data is 3100 Pa (expanded uncertainty of 6300 Pa at
the 95 % level). For the measured temperature, the manufacturer only states that its
accuracy is better than 0.1 K. The mTBD was degassed for about 30 min in a round-
bottomed flask before being fed into the density meter. This was done by placing the
sample in an ultrasonic bath and removing the gases in the system using a vacuum
pump.
The DMA HP density meter was calibrated using nitrogen and water, and the
reference values for these compounds were taken from reference equations of state
[13, 14]. For performing calculations with these equations of state, CoolProp’s [15]
Python package was used. The NIST thermophysical properties calculator [16] also
implements the same equations of state, so CoolProp’s functions were verified by
manually comparing the results of the two programs at multiple temperatures and

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pressures. The values were the same in all instances. The parameters for the calibration
equation were optimized using the differential evolution solver [17] implemented in
the SciPy package [18] for Python. The root mean squared error was used as the
objective function. From the calibration results, the standard uncertainty of the device
was estimated to be 0.040 kg·m−3 (expanded uncertainty of 0.082 kg·m−3 at the 95 %
level).
Measurements were performed on 2 separate days, and the device was cleaned and
refilled before the second set of measurements. Eight of the data points were measured
on both days, and the deviation between these repeat measurements was within the
expanded uncertainty of the device.

2.3 Refractive Index

A Dr. Kernchen Abbemat digital refractometer (Anton Paar, Graz, Austria) was used
for refractive index measurements. This refractometer measures at a wavelength of
598.3 nm. The standard uncertainty of the refractometer was calculated to be 0.00 034
(expanded uncertainty of 0.00 078 at the 95 % level) by using measured and reference
values for water at 25 °C [19].

2.4 Liquid Viscosity

For measuring the viscosity, a LVDVE230 rotational viscometer was used (Brookfield,
Middleboro, MA, USA). The temperature in the measurement cylinder was controlled
using a water bath. For measuring the temperature, probes were placed in the inlet
and outlet of the heating water from the measurement cylinder. The temperature of the
measurement was calculated as the average of these two temperatures. The difference
between the inlet and outlet temperatures was less than 0.05 K at room temperature
and less than 0.2 K at higher temperatures. The viscometer was left to stabilize at
each measurement temperature for at least 30 min before values were recorded. The
viscometer was calibrated using a Brookfield viscosity standard (Lot number 012610),
water, and n-hexadecane. The deviation between the calibrated experimental values
and reference data was used to calculate the uncertainty of the device. The standard
uncertainty was 5.4 %, and the expanded uncertainty (95 % level) was 12 %.
Three measurements were performed for mTBD. The first measurements were
done with a setup that was open to the atmosphere. To confirm that moisture absorbed
from the air did not affect the measurements, a third run was carried out in which
the viscometer was covered with a large piece of flexible plastic that was draped over
the instrument and dry air was continually added to the space around the viscometer.
This lowered the relative humidity around the viscometer during the experiment. The
results of the three different experiments matched to within the uncertainty of the
device, so any absorption of water did not noticeably affect the results.

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2.5 Liquid Vapor Pressure with the Gas Saturation Method

The gas saturation method was used for measuring the vapor pressure of mTBD at
temperatures below 386.16 K [20, 21]. The sample was placed in a glass vessel that
contained spherical glass beads. This vessel was placed in a gas chromatography oven,
which maintained a stable temperature (temperature remained within ± 0.01 K). A
flow of nitrogen was introduced (at 20 mln·min−1 ), which flowed through the cell and
became saturated with the vaporized mTBD. The flow rate of nitrogen was maintained
using a flow controller (Alicat Scientific, Tucson, AZ, USA). The flow rate of the
nitrogen was measured using a bubble meter (standard uncertainty of 0.020 ml·min−1 ,
expanded uncertainty of 0.045 ml·min−1 at the 95 % level). The vessel was held at the
set temperature for a period of time (usually 24 h or more), and then the vessel was
removed and weighed to determine the mass lost. From these data, the vapor pressure
was calculated using Eq. 1
m
P W  · (Patm + Ploss ), (1)
m t V Patm
W + Troom R

where P is the vapor pressure (Pa), m is the mass of the test chemical (mTBD) that
leaves the cell (g), W is the molar mass of the test chemical (g·mol−1 ), t is the duration
of the measurement (min), V is the volumetric flow rate of the carrier gas (in this
case, nitrogen) in units of L·min−1 , Patm is the atmospheric pressure at the place and
time the experiment is carried out (Pa), Troom is room temperature (K), R is the ideal
gas constant, and Ploss is the pressure drop over the gas saturation cell (assumed to
be zero for our measurements). More details about the gas saturation method can be
found from other references [20, 21].
The inlet and outlet of the glass vessel were covered with paraffin film when remov-
ing it from the oven for weighing. This was done to ensure that the mTBD did not
absorb water from the air. Also, when the oven was heating up or cooling down, a
small flow of nitrogen was still applied (0.5 mln·min−1 ) to reduce the amount of out-
side air that entered the cell. When measuring the masses and the flow rate, repeat
measurements were made (usually 8) and the average was recorded as the final value.
Atmospheric pressure was measured using the MC2-PE pressure calibrator. Temper-
atures (both cell and room temperatures) were measured using a Systemteknik S2541
thermometer (Frontec) with calibrated Pt-100 temperature probes (Frontec).
Uncertainties were calculated using a Monte Carlo method (see ISO/IEC Guide
98-3) [22]. Distributions were specified for eight different parameters that could poten-
tially affect the vapor pressure value, including the purity of the mTBD. Values were
then selected from these distributions and used to calculate a vapor pressure value.
This process was repeated 1 million times for each experimental data point, and the
resulting distributions were then used for estimating the uncertainties. The Python code
used for this calculation can be found from the OSF project for this study (https://osf.
io/efds6/).

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2.6 Liquid Vapor Pressure with the Distillation Method

Vacuum distillation was used for measuring the vapor pressure of mTBD at tempera-
tures above 380 K. Two different distillations were performed, one at the University
of Helsinki and one at Aalto University.
The distillation at the University of Helsinki was performed using mTBD that had
already been distilled once. A simple distillation was performed, that is, no column
was used. A water jet pump was used to apply a vacuum, and a needle valve was used
to introduce a small leak to allow the pressure to be regulated. The temperature of
the condensate was measured using a Type K thermocouple, which had an expanded
uncertainty of ± 1 K. The expanded uncertainty of the vacuum gauge was estimated
to be the greater of 10 % or 200 Pa.
At Aalto University, the distillation was performed with the mTBD obtained from
BOC Sciences, which had an initial purity of 97 wt%. A 0.55 m Vigreux column
was used. When measuring the vapor pressure, the column was operated at total
reflux. The condensers were cooled using a circulating bath that was set to 290 K. A
vacuum pump was used to reduce the pressure, and a small leak was introduced using
a needle valve in order to adjust the pressure. The temperature was measured using
a Nokeval temperature probe (Nokia, Finland), which had been calibrated against an
RTD temperature probe that had been calibrated at the Finnish National Metrology
Institute (Espoo, Finland). Based on this calibration, the standard uncertainty of the
temperature probe was estimated to be 0.06 K (expanded uncertainty of 0.12 K at
the 95 % level). A Vacuuview pressure gauge (Vacuubrand, Wertheim, Germany) was
used to measure the pressure. It was calibrated using the MC2-PE pressure calibrator,
and based on this calibration the standard uncertainty was calculated to be 14 Pa
(expanded uncertainty of 31 Pa at the 95 % level).
The overall uncertainty of the vapor pressures measured using distillation was cal-
culated by combining the uncertainties of the temperature measurements and pressure
gauges. This was done using a Monte Carlo method with sampling repeated 1 million
times (see ISO/IEC Guide 98-3) [22].

2.7 Heat Capacity

For the heat capacity measurements, a C80 Calvet calorimeter (Setaram, Caluire,
France) was used. The measurement cell was made of Hastelloy C276 (S60/1512)
and had a volume of 14 mL. The instrument was calibrated using water and
nitrogen. Heat capacity measurements were performed at a constant pressure of
360 000 Pa ± 20 000 Pa. The vapor pressure of mTBD is substantially lower than
the measurement pressure, thus ensuring that the sample is in the liquid phase.
Measurements were performed in a stepwise manner. The temperature was first held
steady at a specified temperature. Then the temperature was increase 10 K, and during
this ramp the difference in temperature between the reference and sample cells was
recorded. The total heat flow for a given step change was calculated via integration,
and the heat capacity was then calculated using Eq. 2 [23]

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CP1 · ρ1 Q2 − Q0
CP2  · . (2)
ρ2 Q1 − Q0

In Eq. 2, ρ 1 is the density for the standard (water in our case); ρ 2 is the density for the
sample; C P1 is the heat capacity of the standard (water); C P2 is the heat capacity of the
sample; and Q0 , Q1 and Q2 are the measured heats of the blank (nitrogen), standard,
and sample, respectively. The reference values for the heat capacity of water were
calculated using the NIST thermophysical properties calculator [16], which is based
on the IAPWS95 equation of state [14]. The temperature was taken as the average of
the initial and final temperature of the step.
The heat capacity of water and a 3 molal aqueous NaCl solution were measured to
check the performance of the calorimeter. Measured data were compared to reference
values from the IAPWS95 equation of state [14], which can be accessed from the
NIST website [16], and to values from Clarke and Glew [24]. Based on this check,
the standard uncertainty of the measurements was calculated to be 0.0028 J·g−1 ·K−1
(expanded uncertainty of 0.0057 J·g−1 ·K−1 at the 95 % level). At temperatures above
373 K, the deviation between measured and reference values increased. The measured
data for water and NaCl can be found from the heat capacity file on the OSF project
page (https://osf.io/zyr5t/).

2.8 Melting Properties

Differential scanning calorimetry (DSC) was used to determine the melting point and
enthalpy of fusion of mTBD. The DSC measurement was performed on a Q2000
DSC instrument (TA Instruments, New Castle, DE, USA) equipped with a two-stage
refrigerated cooling system. Analysis was run on an mTBD sample with a mass of
9.33 mg, which was hermetically sealed in a 50 mg Tzero aluminum pan. The pan
was filled and sealed in a glove box that was filled with dry air to avoid absorption
of water. Inside the DSC chamber, which was filled with N2 , the sample was cooled
(rate 5 K·min−1 ) to 213 K to crystallize the sample and then heated (rate 1 K·min−1 )
to observe the melting point. A lower heating rate provides better correspondence
between the DSC temperature and the actual temperature of the sample. The onset
of the melting peak on the DSC thermogram was taken to be the melting point, and
the heat of fusion was calculated by integrating to find the area of the peak. Based on
reference and measured values for water, acetic acid, and n-hexadecane, the standard
uncertainty of the melting point measurements was calculated to be 0.49 K (expanded
uncertainty of 1.2 K at the 95 % level). The standard uncertainty for the enthalpy
measurement was 10 J·g−1 (expanded uncertainty of 26 J·g−1 at the 95 % level).

2.9 Thermal Conductivity

The transient hot wire method was utilized to measure the thermal conductivity
of mTBD. The device was a THW-L2 Liquid Thermal Conductivity Meter from
Thermtest Inc. (Fredericton, NB, Canada). The THW method assumes isotropic fluids

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and the Fourier heat conduction equation for transient testing can then be formulated
as Eq. 3 [25]
∂T
ρ · Cp ·  λ · ∇2T . (3)
∂t
In Eq. 3, λ is the thermal conductivity, ρ is the density, T is temperature, t is time,
and C p is the specific heat capacity. During testing, the sensor wire is heated with
step-function-like constant effect that lasts less than 2 s, and the resulting temperature
rise is recorded. If the wire length and sample volume can be considered infinite during
the test time, the thermal conductivity can then be calculated from the temperature
rise equation, as derived from Eq. 3:
 
q 4·κ ·t
T (r0 , t)  · ln 2 γ . (4)
4·π ·λ r0 · e

Here κ is the thermal diffusivity, r0 the wire radius, q the heat transfer rate, and γ
is Euler’s constant [26, 27]. However, the experimental setup deviates from an ideal
system and the results are therefore corrected with an offset calibration, which allows
for accurate testing of the thermal conductivity but hinders accurate measurement of
the diffusivity. For calibration, deionized water was used.
The expanded uncertainty of the measured values was estimated to be 5 %, which
for the values presented here is ± 0.007 W·m−1 ·K−1 .
For successful testing of the mTBD samples, a stainless-steel container was used
to hold the sample. Aluminum had to be avoided because corrosion occurred with
aqueous solutions of mTBD. To prevent degradation of the probe structure, the sensor
body was coated with epoxy. About 25 mL of the sample was used for each test.
Testing was performed at 298 K, 323 K, 348 K, and 373 K.

2.10 Modeling Using PC-SAFT Equation of State

The PC-SAFT equation of state was used to model the properties of mTBD and three
of the compounds used for comparison: 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU), and 1,1,3,3-tetramethylguanidine (TMG).
Our code for implementing PC-SAFT is available on GitHub (https://github.com/
zmeri/PC-SAFT). We verified our code to ensure we got results that matched refer-
ence data and the values given by PC-SAFT code from other authors, and the code to
perform these checks is included in the GitHub repository.
The PC-SAFT parameters were determined by optimizing the equation of state
parameters using vapor pressure and density data. For mTBD, the experimental data
presented in this article were used. Literature data were used for DBN, DBU, and
TMG [28–32]. To solve for the parameters, we used the differential evolution solver
[17] implemented in the SciPy package [18] for Python. For the objective function,
the root mean squared error of the vapor pressure and density values were calculated
separately and then these were added together to get a final error value to minimize.

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Fig. 2 Density of mTBD as a function of pressure and temperature

DBN and DBU are polar molecules with dipole moments of about 3 Debye, so for
these compounds Gross and Vrabec’s polar term was included in the PC-SAFT model
[33]. Cripwell et al. [34] showed that more reliable parameters for the polar term can
be determined if vapor–liquid equilibrium data are included for mixtures of the polar
compound with a non-polar compound. However, since no such data are available for
DBN and DBU, the number of dipoles was set to be 1, as originally specified by Gross
and Vrabec.

3 Results and Discussion

3.1 Liquid Compressed Density and Derivative Properties

The experimental density data are shown in Fig. 2. The density was measured at tem-
peratures from 293.15 K to 473.15 K and at pressures from 0.092 MPa to 15.788 MPa.
A file containing these data can be found from the Open Science Framework page for
this project (https://osf.io/z4b2p/) and in Table 2. No density data were found in the
scientific literature. The only value we could find came from the safety data sheets
for mTBD, which state that the density at 298 K is 1067 kg·m−3 . Although this is
in the same range as the value we obtained (1063.35 ± 0.082 kg·m−3 at 298 K and
101 000 Pa), the difference is still several times larger than the expanded uncertainty
of our data.
A polynomial equation (Eq. 5) was fit to the density data so that density could be
calculated more accurately than with the PC-SAFT equation of state

ρ  C1 + C2 · T + C3 · P + C4 · P 2 + C5 · T · P + C6 · T 2 + C7 · T 2 · P + C8 · T · P 2 + C9 · T 3 .
(5)

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Table 2 Compressed densities of mTBD, thermal expansion coefficient, and isothermal compressibility

Temperature Pressure Density Thermal Expanded Isothermal Expanded

(K) (MPa) (kg·m−3 ) expansion uncertainty compress- uncertainty of
coefficient of thermal ibility isothermal
(K−1 ) expansion (MPa−1 ) compressibility
coefficient (MPa−1 )
(K−1 )

293.15 0.092 1067.24 7.32E−04 1.3E−06 4.72E−04 8.9E−06

293.15 1.975 1068.21 7.28E−04 1.2E−06 4.63E−04 7.0E−06
293.15 3.956 1069.15 7.24E−04 1.2E−06 4.53E−04 5.2E−06
293.15 5.934 1070.13 7.20E−04 1.1E−06 4.43E−04 3.6E−06
293.15 7.911 1071.05 7.16E−04 1.1E−06 4.33E−04 2.8E−06
293.15 9.885 1071.9 7.13E−04 1.1E−06 4.23E−04 3.5E−06
293.15 11.858 1072.79 7.09E−04 1.1E−06 4.13E−04 5.0E−06
293.15 13.823 1073.62 7.06E−04 1.2E−06 4.03E−04 6.8E−06
293.15 15.786 1074.48 7.02E−04 1.3E−06 3.93E−04 8.6E−06
298.15 1.980 1064.27 7.31E−04 1.1E−06 4.73E−04 6.6E−06
298.15 5.927 1066.2 7.23E−04 9.9E−07 4.52E−04 3.3E−06
298.15 9.877 1068.09 7.15E−04 9.8E−07 4.32E−04 3.2E−06
298.15 15.781 1070.77 7.04E−04 1.1E−06 4.02E−04 8.3E−06
298.15 0.091 1063.33 7.35E−04 1.2E−06 4.83E−04 8.5E−06
298.15 1.002 1063.82 7.33E−04 1.1E−06 4.78E−04 7.6E−06
298.15 13.819 1069.9 7.08E−04 1.0E−06 4.12E−04 6.5E−06
298.15 15.785 1070.76 7.04E−04 1.1E−06 4.02E−04 8.3E−06
298.15 1.983 1064.34 7.31E−04 1.1E−06 4.73E−04 6.6E−06
298.15 2.968 1064.82 7.29E−04 1.0E−06 4.68E−04 5.7E−06
298.15 3.957 1065.34 7.27E−04 1.0E−06 4.63E−04 4.9E−06
298.15 4.946 1065.8 7.25E−04 1.0E−06 4.58E−04 4.1E−06
298.15 5.935 1066.31 7.23E−04 9.8E−07 4.52E−04 3.3E−06
298.15 6.920 1066.77 7.21E−04 9.8E−07 4.47E−04 2.8E−06
298.15 7.909 1067.23 7.19E−04 9.7E−07 4.42E−04 2.5E−06
298.15 8.896 1067.68 7.17E−04 9.7E−07 4.37E−04 2.7E−06
298.15 9.884 1068.13 7.15E−04 9.9E−07 4.32E−04 3.2E−06
298.15 10.869 1068.58 7.14E−04 1.0E−06 4.27E−04 3.9E−06
298.15 11.855 1069.02 7.12E−04 1.0E−06 4.22E−04 4.7E−06
323.15 0.092 1043.69 7.55E−04 6.3E−07 5.42E−04 6.8E−06
323.15 0.516 1043.93 7.53E−04 6.0E−07 5.39E−04 6.5E−06
323.15 1.977 1044.79 7.50E−04 5.0E−07 5.31E−04 5.4E−06
323.15 3.956 1045.87 7.45E−04 4.4E−07 5.20E−04 3.9E−06
323.15 5.933 1046.94 7.39E−04 4.1E−07 5.09E−04 2.6E−06
323.15 7.910 1048 7.35E−04 4.1E−07 4.98E−04 1.9E−06
323.15 9.886 1049 7.30E−04 4.2E−07 4.87E−04 2.5E−06

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Table 2 continued

Temperature Pressure Density Thermal Expanded Isothermal Expanded

(K) (MPa) (kg·m−3 ) expansion uncertainty compress- uncertainty of
coefficient of thermal ibility isothermal
(K−1 ) expansion (MPa−1 ) compressibility
coefficient (MPa−1 )
(K−1 )

323.15 11.855 1049.99 7.25E−04 4.5E−07 4.76E−04 3.8E−06

323.15 13.824 1050.96 7.20E−04 5.0E−07 4.65E−04 5.3E−06
323.15 15.786 1051.93 7.16E−04 6.3E−07 4.54E−04 6.8E−06
348.15 11.856 1030.95 7.40E−04 3.4E−07 5.42E−04 3.7E−06
348.15 13.824 1032.03 7.35E−04 3.8E−07 5.30E−04 4.9E−06
348.15 15.786 1033.11 7.29E−04 4.9E−07 5.18E−04 6.2E−06
348.15 0.087 1023.91 7.76E−04 4.6E−07 6.14E−04 6.3E−06
348.15 1.978 1025.09 7.70E−04 3.5E−07 6.03E−04 5.0E−06
348.15 3.954 1026.31 7.64E−04 3.2E−07 5.90E−04 3.7E−06
348.15 5.933 1027.52 7.58E−04 3.2E−07 5.78E−04 2.6E−06
348.15 7.911 1028.67 7.52E−04 3.3E−07 5.66E−04 2.1E−06
348.15 9.885 1029.81 7.46E−04 3.3E−07 5.54E−04 2.6E−06
373.15 1.977 1005.3 7.94E−04 4.7E−07 6.88E−04 5.3E−06
373.15 15.788 1014.31 7.44E−04 5.5E−07 5.96E−04 6.8E−06
373.15 3.930 1006.66 7.86E−04 4.5E−07 6.75E−04 4.0E−06
373.15 7.884 1009.3 7.72E−04 4.7E−07 6.49E−04 2.5E−06
373.15 15.764 1014.35 7.44E−04 5.4E−07 5.97E−04 6.7E−06
373.15 13.822 1013.03 7.51E−04 4.8E−07 6.09E−04 5.4E−06
373.15 11.855 1011.8 7.58E−04 4.7E−07 6.22E−04 4.1E−06
373.15 7.908 1009.22 7.72E−04 4.8E−07 6.49E−04 2.5E−06
373.15 9.883 1010.51 7.65E−04 4.7E−07 6.36E−04 3.0E−06
373.15 3.954 1006.68 7.86E−04 4.6E−07 6.75E−04 4.0E−06
373.15 5.932 1008.03 7.79E−04 4.7E−07 6.62E−04 2.9E−06
373.15 1.976 1005.33 7.94E−04 4.7E−07 6.88E−04 5.3E−06
373.16 0.098 1004 8.01E−04 5.3E−07 7.01E−04 6.6E−06
398.15 9.857 991.11 7.86E−04 4.8E−07 7.32E−04 3.2E−06
398.15 11.827 992.54 7.78E−04 4.7E−07 7.18E−04 4.5E−06
398.15 13.795 993.97 7.70E−04 4.9E−07 7.04E−04 6.2E−06
398.15 0.091 983.79 8.28E−04 5.6E−07 8.03E−04 7.7E−06
398.15 1.956 985.23 8.20E−04 4.8E−07 7.90E−04 6.0E−06
398.15 15.758 995.35 7.62E−04 5.7E−07 6.89E−04 7.8E−06
398.15 7.882 989.67 7.95E−04 4.6E−07 7.46E−04 2.6E−06
398.15 1.979 985.22 8.20E−04 4.9E−07 7.90E−04 6.0E−06
398.15 3.928 986.76 8.11E−04 4.6E−07 7.75E−04 4.4E−06
398.15 5.907 988.24 8.03E−04 4.6E−07 7.61E−04 3.2E−06
423.14 9.853 971.53 8.10E−04 3.9E−07 8.44E−04 3.5E−06

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Table 2 continued

Temperature Pressure Density Thermal Expanded Isothermal Expanded

(K) (MPa) (kg·m−3 ) expansion uncertainty compress- uncertainty of
coefficient of thermal ibility isothermal
(K−1 ) expansion (MPa−1 ) compressibility
coefficient (MPa−1 )
(K−1 )

423.14 11.824 973.14 8.01E−04 4.2E−07 8.28E−04 5.3E−06

423.14 0.090 963.3 8.59E−04 5.9E−07 9.22E−04 9.8E−06
423.15 1.973 964.87 8.49E−04 4.7E−07 9.07E−04 7.6E−06
423.15 13.791 974.7 7.92E−04 4.9E−07 8.13E−04 7.3E−06
423.15 15.755 976.23 7.83E−04 6.4E−07 7.98E−04 9.5E−06
423.15 3.923 966.61 8.39E−04 3.9E−07 8.91E−04 5.4E−06
423.15 5.902 968.27 8.30E−04 3.6E−07 8.75E−04 3.5E−06
423.16 7.881 969.88 8.20E−04 3.8E−07 8.60E−04 2.6E−06
423.16 1.949 964.85 8.49E−04 4.7E−07 9.07E−04 7.7E−06
473.14 5.898 927.56 8.92E−04 1.4E−06 1.16E−03 6.4E−06
473.14 7.875 929.67 8.80E−04 1.4E−06 1.14E−03 5.2E−06
473.15 0.062 921.05 9.30E−04 1.7E−06 1.21E−03 1.5E−05
473.15 1.972 923.2 9.18E−04 1.5E−06 1.20E−03 1.2E−05
473.15 3.919 925.4 9.05E−04 1.5E−06 1.18E−03 9.0E−06
473.15 13.788 935.74 8.43E−04 1.6E−06 1.08E−03 1.1E−05
473.15 15.751 937.7 8.31E−04 1.7E−06 1.06E−03 1.5E−05
473.15 9.851 931.74 8.67E−04 1.4E−06 1.12E−03 6.1E−06
473.15 11.82 933.78 8.55E−04 1.5E−06 1.10E−03 8.4E−06
473.15 3.919 925.38 9.05E−04 1.5E−06 1.18E−03 9.0E−06

Standard uncertainty of the density: u(density)  0.040 kg·m−3 (expanded uncertainty u(density) 
0.082 kg·m−3 at the 95 % level). Standard uncertainty of temperature u(temperature)  0.1 K (expanded
uncertainty u(temperature)  0.2 K at the 95 % level). The standard uncertainty of the pressure is u(pressure)
 3100 Pa (expanded uncertainty u(pressure)  6300 Pa at the 95 % level)

In Eq. 5, ρ is the density (kg·m−3 ), T is the temperature (K), P is the pressure

(MPa), and the C values are constants. These equation constants are given in Table 3.
This equation is valid over the range of the experimental density data, so from 293 K
to 473 K and from 90 000 Pa to 15 700 000 Pa. The root mean squared error (RMSE)
of Eq. 5 is 0.035 kg·m−3 , when compared to the experimental data, and the maximum
deviation was 0.073 kg·m−3 . The constants were determined using the differential
evolution solver [17] implemented in the SciPy package [18] for Python.
Using this more accurate polynomial fit, derivative properties could be calculated
more reliably than with the PC-SAFT equation of state. The thermal expansion coef-
ficient and the isothermal compressibility were calculated by taking the appropriate
derivatives of Eq. 5, and the resulting data are also given in the same file as the den-
sity data (https://osf.io/jb8y7/). The expanded uncertainties of the thermal expansion
coefficient and the isothermal compressibility were calculated using the same Monte

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Table 3 Constants for C1 1.29 934 399 × 103

polynomial density equation
C2 − 8.40 839 641 × 10−1
C3 7.71 488 318 × 10−1
C4 − 5.84 175 802 × 10−4
C5 − 3.58 906 385 × 10−3
C6 2.96 880 106 × 10−4
C7 9.13 797 725 × 10−6
C8 − 6.89 083 285 × 10−6
C9 − 4.42 874 998 × 10−7

Fig. 3 Comparison of the densities of mTBD and other similar compounds at 0.1 MPa. The x markers
indicate experimental data points. (mTBD, , this work; DBN, , [29]; DBU, , [30]; TMG, , [31]), the
lines indicate model: mTBD, ; DBN, ; DBU, ; TMG, ;1-methylnaphthalene [35], (Color figure
online)

Carlo method used for calculating the vapor pressure uncertainties. The Python code
used for this calculation can be found from the OSF project for this study (https://osf.
io/273tq/).
We compared the density of mTBD to that of some structurally similar compounds,
as shown in Fig. 3. For DBN, DBU and TMG PC-SAFT parameters were fit in this
study using literature data [29–33] (see Sect. 3.7), and PC-SAFT was then used for
calculating values for comparison. The one exception was 1-methylnaphthalene, for
which values were taken from the DIPPR correlation [35]. mTBD had a higher density
than any of the compounds considered in this work.

3.2 Vapor Pressure of Liquid

The vapor pressure was measured at temperatures from 318.23 K to 451.2 K and
pressures from 11.1 Pa to 10 000 Pa. The measurements were conducted with two

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International Journal of Thermophysics (2019) 40:71 Page 15 of 23 71

Fig. 4 Vapor pressure of mTBD and comparison with some other compounds. The markers indicate experi-
mental data points (mTBD, ; DBN, ; DBU, ; TMG, ), the lines indicate model: mTBD, ; DBN, ;
DBU, ;TMG, ;1-methylnaphthalene [35], (Color figure online)

methods: the gas saturation method and the distillation method. The experimental
vapor pressure data are shown in Fig. 4 and in Table 4. A complete data file can be
obtained from the OSF page for this project (https://osf.io/t64dn/), and this file contains
the calculations for the gas saturation data. The values for several structurally similar
compounds were also plotted for comparison. For most of these other compounds, the
values for comparison were calculated using PC-SAFT. The PC-SAFT parameters for
these compounds were fit in this study using literature data. For 1-methylnaphthalene,
the vapor pressure was calculated using the DIPPR correlation [35].
No vapor pressure data can be found for mTBD in the literature. Some safety data
sheets give a single vapor pressure value of 0.1 hPa (or 0.1 mmHg, depending on the
sheet) at 348 K to 352 K. This value is significantly lower than the data measured in
this study, which could present a safety issue if the actual vapor pressure is higher than
expected.
However, some data for structurally similar compounds can be found in the liter-
ature. For comparison, the vapor pressures of these compounds (DBN, DBU, TMG,
and 1-methylnaphthalene) are also given in Fig. 4, and as seen, mTBD has a rela-
tively low vapor pressure compared to these other compounds. DBN and DBU can be
considered substitutes for mTBD in many applications because they also have similar
basic properties and form ionic liquids, so the lower vapor pressure of mTBD may be
one factor in deciding which compound to use.
Another interesting comparison is between mTBD and the closely related com-
pound 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). Although no vapor pressure data
are publicly available for TBD, when distilling the mTBD the residue in the bottom
was enriched in TBD, which indicates that TBD has an even lower vapor pressure than
mTBD.

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Table 4 Liquid vapor pressure of mTBD

Temperaturea (K) Vapor pressure (Pa) Expanded uncertainty of vapor Measurement method
pressure at 95 % level (Pa)

318.23 11.1 0.13 Gas saturation

328.21 22.4 0.27 Gas saturation
338.21 45.2 0.54 Gas saturation
348.20 87.2 1.1 Gas saturation
348.22 85.6 1.0 Gas saturation
363.23 213 2.6 Gas saturation
369.2 300 200 Distillation (Helsinki)
386.16 722 12 Gas saturation
386.7 742 28 Distillation (Aalto)
398.0 1287 28 Distillation (Aalto)
404.4 1662 29 Distillation (Aalto)
411.6 2354.5 30 Distillation (Aalto)
419.2 3300 330 Distillation (Helsinki)
425.2 4300 430 Distillation (Helsinki)
431.2 5100 510 Distillation (Helsinki)
433.2 5600 560 Distillation (Helsinki)
436.2 6100 610 Distillation (Helsinki)
438.2 6500 650 Distillation (Helsinki)
445.2 7900 790 Distillation (Helsinki)
448.2 8800 880 Distillation (Helsinki)
451.2 10 000 1000 Distillation (Helsinki)
u(Tgas saturation )  0.04 K, u(Tdistillation, Helsinki )  1 K, u(Tdistillation Aalto )  0.12
a The expanded uncertainty of the temperature measurements (at the 95 % level)

3.3 Liquid Viscosity

The liquid viscosity (290.79 K to 363.00 K and atmospheric pressure) is presented in

Fig. 5 and Table 5. The data were fit using Eq. 6, which is a form of the Andrade and
DIPPR equations [35, 36]. The differential evolution solver [17] implemented in the
SciPy package [18] for Python was used to fit the parameters for Eq. 6.
B
ln(η)  A + + C · ln(T ). (6)
T
In Eq. 6, η is the dynamic viscosity (mPa·s), T is the temperature (K), and A through
C are constants. The constants fit to the data for mTBD are as follows: A  − 118.97,
B  7767.2, and C  16.653. The root mean squared error of Eq. 6 was 4 %, and the
maximum deviation from the experimental data was 12 %.
The viscosity of 1-methylnaphthalene and TMG were also plotted in Fig. 5 for
comparison, and mTBD has a higher viscosity than either of these compounds.

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International Journal of Thermophysics (2019) 40:71 Page 17 of 23 71

Fig. 5 Viscosity of mTBD ( ) at 0.1 MPa and comparison with data for TMG [32], ; and 1-
methylnaphthalene [35], ; mTBD Eq. 6, (Color figure online)

Table 5 Viscosity of mTBD at pressure 0.1 MPa

Temperature (K)a Viscosity (mPa·s)b Temperature (K) Viscosity (mPa·s)

296.54 7.1 305.92 5.7

290.79 9.6 313.58 4.1
290.93 9.6 328.48 3.3
302.83 6.5 338.46 2.7
318.08 4.3 347.79 2.3
323.34 3.8 362.83 1.8
323.35 3.8 294.45 7.9
333.35 3.0 299.18 6.7
342.02 2.6 307.06 5.3
356.51 2.0 317.49 4.1
363.00 1.8 332.05 2.9
294.95 7.9 346.91 2.2
300.14 6.7 360.49 1.8
u(p)  10 kPa, standard uncertainty
a The expanded uncertainty of the temperature increases linearly from 0.04 K at 293 K up to 0.2 K at 363 K
b Standard uncertainty of viscosity: 5.4 %; expanded uncertainty (95 % level): 12 %

3.4 Melting Point and Heat of Fusion

The melting point of mTBD was measured to be 290 ± 1.2 K and the heat of fusion is
70 ± 25 J·g−1 . The thermogram from the DSC measurement is given in Fig. 6. When
handling mTBD, we also noticed it can exist for months in a subcooled state. We stored
the mTBD samples in the fridge at 277 ± 2 K and did not observe freezing. However,
when cooled to lower temperatures, the mTBD would freeze and remain solid in the
fridge.

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Fig. 6 DSC thermogram showing the melting peak of mTBD

3.5 Liquid Heat Capacity

The experimental data for the isobaric liquid heat capacity at 0.36 MPa are given
in Table 6 and shown in Fig. 7. Equations of state, such as PC-SAFT, generally only
provide the residual heat capacity, and a separate relationship for the ideal gas contribu-
tion is needed [15]. Usually ideal gas heat capacities are calculated using a statistical
mechanical model and/or spectroscopic data [13, 37]. Because such data were not
available, we instead used the PC-SAFT equation of state to calculate the residual
heat capacity and then subtracted this from the experimental data to determine the
ideal gas heat capacity. These ideal gas heat capacity values were then correlated
using the Aly–Lee equation (Eq. 7) [37, 38]
 2  2
C/T E/T
Cpid  A + B +D . (7)
sin h(C/T ) cos h(E/T )

In Eq. 7, Cid −1 −1
p is the ideal gas heat capacity (J·kmol ·K ), T is the temperature (K),
and A through E are constants. Note that the units for heat capacity are J·kmol−1 ·K−1 .
The constants for mTBD are given in Table 7.
Because we used an equation of state to calculate the ideal gas heat capacities, any
uncertainty from the equation of state is carried over to these ideal gas values. Gross
and Sadowski [10] calculated heat capacities for seven compounds using PC-SAFT,
and they found that on average the deviation from reference data was 1.7 %. So the
ideal gas heat capacities given here likely have an uncertainty in the same range.
To improve the performance of the PC-SAFT model when extrapolated above
392 K, the constants C, D, and E of the Aly–Lee equation were set to be similar
to values found in the DIPPR database [35] for the structurally similar compounds
naphthalene and 1-methylnaphthalene. Setting these three constants resulted in a trend
that is still at least qualitatively correct at higher temperatures. When all five constants

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International Journal of Thermophysics (2019) 40:71 Page 19 of 23 71

Table 6 Liquid isobaric heat capacity at pressure 0.36 MPa and ideal gas heat capacity of mTBD

Temperaturea (K) Heat capacity Heat capacity Ideal gas heat capacity
(J·mol−1 ·K−1 ) (J·g−1 ·K−1 )b (J·mol−1 ·K−1 )

312.33 275.8 1.800 193

312.48 275.8 1.800 193
322.24 279.6 1.825 198
322.38 280.3 1.829 199
332.14 284.9 1.860 205
332.28 285.5 1.863 206
342.03 289.7 1.891 212
342.17 290.4 1.895 212
351.93 294.9 1.924 218
352.06 295.3 1.927 219
361.82 299.6 1.955 224
361.96 299.9 1.957 225
371.71 304.2 1.986 230
371.85 304.4 1.987 230
381.61 309.1 2.017 236
381.74 309.2 2.018 236
391.50 313.8 2.048 242
391.63 313.5 2.046 242
u(p)  0.01 MPa, standard uncertainty
a u(temperature)  0.05 K, standard uncertainty
b The standard uncertainty of the heat capacity is 0.0028 J·g−1 ·K−1 (expanded uncertainty of
0.0057 J·g−1 ·K−1 at the 95 % level). The standard uncertainty for the Ideal gas heat capacity is
4.2 J·mol−1 ·K−1 . (expanded uncertainty of 8.6 J·mol−1 ·K−1 at the 95 % level)

were optimized, instead of just 2, the Aly–Lee equation gave decreasing heat capacity
values above 392 K and had a shape that was clearly incorrect.

3.6 Liquid Thermal Conductivity and Refractive Index

The experimental data for the liquid thermal conductivity of mTBD are given in
Table 8.
The refractive index of mTBD was measured between 293 K and 343 K. The results
are presented in Table 9.

3.7 Modeling Using PC-SAFT

The PC-SAFT equation of state reproduced the experimental data well, with an average
relative deviation of 0.24 % for density and 2.4 % for vapor pressure. The PC-SAFT
parameters determined for mTBD, as well as those for DBN, DBU, and TMG, are

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Fig. 7 Liquid isobaric heat capacity of mTBD ( ) and the values calculated using PC-SAFT, –. Ideal gas
heat capacities calculated using the Aly–Lee equation ( ) are also shown (Color figure online)

Table 7 Constants for Aly–Lee equation for mTBD

A 113 860
B 338 600
C 700
D 100 000
E 3500
Constants C, D, and E were fixed based on values for structurally similar compounds. Only A and B were
optimized

Table 8 Liquid thermal conductivity of mTBD at pressure 0.1 MPa

Temperaturea (K) Thermal conductivityb (W·m−1 ·K−1 )

299.0 0.144
323.8 0.140
348.2 0.137
372.9 0.138
u(p)  10 kPa, standard uncertainty
a u(temperature)  0.5 K, standard uncertainty
b u(thermal Conductivity), expanded uncertainty of 0.007 W·m−1 ·K−1

given in Table 10. Using PC-SAFT, it was possible to estimate the normal boiling
point of mTBD, which was calculated to be 536 K. The enthalpy of vaporization can
also be calculated using the equation of state and at 298.15 K it is 67.7 kJ·mol−1 .

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International Journal of Thermophysics (2019) 40:71 Page 21 of 23 71

Table 9 Measured liquid refractive index of mTBD at pressure 0.1 MPa

Temperaturea (K) Refractive index

293.15 1.5381
298.15 1.5357
303.15 1.5338
313.15 1.5295
323.15 1.5253
333.15 1.5211
343.15 1.5168
Standard uncertainty of liquid refractive index: u(refractive index)  0.00034, (expanded uncertainty of
0.000078 at the 95 % level)
u(p)  10 kPa, standard uncertainty
a u(T)  0.03 K, standard uncertainty

Table 10 PC-SAFT parameters for mTBD, DBN, DBU, and TMG

Molar mass m σ ε/k μa nμ AAD% Data refs.

(g· mol−1 )
Psat ρ

mTBD 153.225 4.1308 3.6822 323.47 – – 2.4 0.24 This work

DBN 124.187 4.5924 3.3138 280.37 3.29a 1 4.3 0.14 [28, 29]
DBU 152.241 3.8212 3.8274 328.98 3.41a 1 4.3 0.17 [28–30]
TMGb 115.18 4.4477 3.3652 251.45 – – 0.0080b 0.047 [31, 32]

m is the segment number, σ is the segment diameter (Å), ε/k is the dispersion energy divided by the
Boltzmann constant (K), μ is the dipole moment, and nμ is the number of dipole moments
a Dipole moments taken from Chalvet et al. [39]
b Only two vapor pressure and six density points were available for TMG

Table 11 Summary of the Molar mass 153.225 g·mol−1

properties of mTBD
Density at 298.15 K and 101 000 Pa 1063.35 kg·m−3
Normal boiling pointa 536 K
Enthalpy of vaporization at 298.15 Ka 67.7 kJ·mol−1
Melting point 290 K
Enthalpy of fusion 70 J·g−1
Viscosity at 298.15 K 7.1 mPa·s
Heat capacity at 298.15 Ka 1.75 J·g−1 ·K−1
Thermal conductivity at 299.0 K 0.144 W·m−1 ·K−1
a Calculated using PC-SAFT
Refractive index at 298.15 K 1.5357
equation of state

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4 Conclusions

This comprehensive study gives the first data on many of the physical and thermody-
namic properties of mTBD. Measured data on the liquid vapor pressure, compressed
density, liquid heat capacity, melting properties, liquid thermal conductivity, refractive
index, and liquid viscosity of mTBD are presented. The experimental data were used
to calculate other properties of mTBD: enthalpy of vaporization, thermal expansion,
and isothermal compressibility. Based on these data and the PC-SAFT model fit to the
data, the properties of mTBD can be summarized (Table 11). PC-SAFT parameters
for several structurally similar compounds were also fit as part of this study, which
allowed comparison. mTBD had a higher density and lower vapor pressure than DBN,
DBU, and TMG.

Acknowledgments Open access funding provided by Aalto University.

Funding Funding was provided by Business Finland (Grant No. 560/31/2017).

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Affiliations

Zachariah Steven Baird1 · Artur Dahlberg1 · Petri Uusi-Kyyny1 ·

Nahla Osmanbegovic1 · Joanna Witos2,3 · Jussi Helminen2 ·
Daniel Cederkrantz4 · Paulus Hyväri2 · Ville Alopaeus1 · Ilkka Kilpeläinen2 ·
Susanne K. Wiedmer2,3 · Herbert Sixta3

1 Department of Chemical and Metallurgical Engineering, Aalto University,

P.O. Box 16100, 00076 Espoo, Finland
2 Department of Chemistry, University of Helsinki, P. O. Box 55, 00014 Helsinki, Finland
3 Department of Bioproducts and Biosystems, Aalto University, P. O. Box 16300, 00076 Espoo,
Finland
4 Thermtest Europe AB, 432 68 Veddige, Sweden

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