2. Compounds Found in
Molecular Electronic Articles
While viewing selected presentations on the nanoHUB website, the same
organic compounds are used in almost every SAM procedure. Also, one
metallic solid is used.
They are: Dodecanethiol, Ethanol, Tetrahydrofuran (THF), Ammonium
Hydroxide, and Gold.
3. What is Nano-Thermodynamics?
First, thermodynamics is the investigation of
changes in energy coming from a physical or
chemical reaction.
Gibbs Free Energy
G = H – T(S)
The thermodynamic variables of enthalpy (H),
entropy (S), and free energy (G) are used in
the Gibbs free energy equation.
4. What is
Nanothermodynamics?
Nano-thermodynamics studies these same changes.
The two differences are chemical potential and an
ensemble term.
G = H – T(S) + [Σ(μ·dn)] + (E·dN)
Nanothermodynamics connects nanosystems to macroscale thermodynamics
5. What is Nano-thermodynamics?
The chemical potential term, [Σ(μ·dn)] was
added by Gibbs in 1961
The symbols μ is the chemical potential and n is the
amount in moles.
Hill included the nano-thermodynamics term
which is added at the ensemble level of the
system, [E·dN].
The variable E is similar to a system’s chemical
potential. The variable N is the number of
individual systems in that one solution component.
An ensemble of N equivalent and noninteracting small
systems is itself a macroscopic system.
6. What is Nano-
thermodynamics?
Usefull in analyzing both experimental and
theoretical equilibrium properties of
nanosystems
Ex. Mean field cluster model of ferromagnetism
(ref.6)
For a thorough treatment of the theory and
derivations of the equation, see reference 4.
7. When did this idea begin?
The idea and the study of small systems at
equilibrium can be traced back to Terrell L.
Hill.
From 1961 to 1963, Hill researched these
small systems in great detail.
Without being aware of it, he was researching
ways to connect macro-thermodynamic
systems to nano-thermodynamic systems.
He published his results in 1962 and 1963, but
little attention was given to it since it was
based on theoretical and statistical models.
Nanoscience was not yet discovered.
8. New attention for an old topic?
In recent years, research in nanoscience has
caught up with Hill’s theoretical work.
In 2000, R.V. Chamberlin, who was investigating
ferromagnetism, was one of the first scientist
to use nanothermodynamic theory to explain
his findings.
Hill reexamined nanothermodynamics as a
useful tool for nano-systems at equilibrium.
9. Nanothermodynamics Today
Professor Hill’s theories have been published in
“Thermodynamics of Small Systems.” (Ref. 8)
R. Chamberlin was instrumental in reviving interest in
small system thermodynamics.
In 2005, A link was established between Hill’s
nanothermodynamics and Tsallis (nonextensive)
thermodynamics. (Ref. 10)
10. Nanothermodynamics Today
Since this area is still new, few articles about this subject are available.
Nanothermodynamics has the potential to be an important contributor to
nanoscience and technology
11. Physical Data & Thermodynamic Properties of
Common Compounds Used in Nanoscience
Dodecanethiol (C12H26S)
M.W.: 202.4 g/mol
M.P
.: unknown
B.P.: 143.5 °C at 15 mmHg
Density: 0.8435 g/cm3 at 20 °C
Solubility: Soluble in ethanol,
ethyl ether and chloroform.
Insoluble in water.
Enthalpy (H) = -253.3 kJ/mol
Entropy (S) = 689.9 J/mol·K
Gibbs (G) = 78.01 kJ/mol
Ethanol (CH3-CH2-OH)
M.W.: 46.07 g/mol
M.P
.: -114.1 °C at 760 mmHg
B.P.: 78.2 °C at 760 mmHg
Density: 0.7893 g/cm3 at 20 °C
Solubility: Miscible in water,
ethanol, ethyl ether and
acetone.
Enthalpy (H) = -277.6 kJ/mol
Entropy (S) = 160.7 J/mol·K
Gibbs (G) = -174.8 kJ/mol
12. Physical Data & Thermodynamic
Properties, Cont.
Tetrahydrofuran (THF):
C4H8O
M.W.: 72.11 g/mol
M.P.: -108.3 °C at 760
mmHg
B.P.: 65 °C at 760 mmHg
Density: 0.8892 g/cm3at 20
°C
Solubility: Soluble in water.
Very soluble in ethanol,
ethyl ether and acetone.
Enthalpy (H) = -216.2
kJ/mol
Entropy (S) = 204.3
J/mol·K
Gibbs (G) =
Ammonium Hydroxide:
NH4OH
M.W.: 35.05 g/mol
M.P.: -77 °C
B.P.: 36 °C
Density: Approx. 0.9 g/mL
Solution Conc.: 14.8 mol/L
13. Physical Data & Thermodynamic
Properties, Cont.
Gold (Element Symbol:
Au)
Atomic Number: 79
M.W.: 196.96 g/mol
M.P.: 1064.18 °C
B.P
.: 2856 °C
Specific Gravity: 19.3
at 20 °C
Solubility: Aqua Regia
H (Fusion): 12.7
kJ/mol
H (Vaporization):
343.1kJ/mol
Reference:
CRC Handbook of Chemistry &
Physics, 2001-2002
Helgeson, H.C.; Owen, C.E.;
Knox, A.M.; Richard, L.
Geochim. Cosmochim. Acta,
1998, 62, 6, 985
14. References
1. CRC Handbook of Chemistry & Physics, 2001-2002
2. Helgeson, H.C.; Owen, C.E.; Knox, A.M.; Richard, L. Geochim. Cosmochim.
Acta, 1998, 62, 6, 985
3. Hill, T.L. J. Chem. Phys. 1962, 36, 3182
4. Hill, T.L. Nano Letters, 2001, 1, 273
5. Hill, T.L. Nano Letters, 2001, 1, 111
6. Hill, T.L. Nano Letters, 2001, 1, 159
7. Hill, T.L.; Chamberlin, R.V. Proc. Natl. Acad. Sci. U.S.A. 1998, 95,
12779
8. Hill, T.L. Thermodynamics of Small Systems; Dover: New York, 1994
9. Chamberlin, R.V. Nature 2000, 408, 337
10. Garcia-Morales, V., Cervera, J., & Pellicer, J. Physics Letter A,
2005, 336, 82
