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Related Concept Videos

States of Water01:23

States of Water

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Water exists in any one of the three classical states: solid (ice), liquid (water), and gas (steam or water vapor). The state of water depends on i) the intermolecular forces that draw molecules together and ii) the kinetic energy that leads to movements that pull them apart.
Water freezes when the intermolecular forces are greater than the kinetic energy. Unlike most other substances, water is less dense in its solid state than in its liquid state. This is because each water molecule can form...
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Comparing Intermolecular Forces: Melting Point, Boiling Point, and Miscibility02:34

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Intermolecular forces are attractive forces that exist between molecules. They dictate several bulk properties, such as melting points, boiling points, and solubilities (miscibilities) of substances. Molar mass, molecular shape, and polarity affect the strength of different intermolecular forces, which influence the magnitude of physical properties across a family of molecules.
Temporary attractive forces like dispersion are present in all molecules, whether they are polar or nonpolar. They...
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Heating and Cooling Curves02:44

Heating and Cooling Curves

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When a substance—isolated from its environment—is subjected to heat changes, corresponding changes in temperature and phase of the substance is observed; this is graphically represented by heating and cooling curves.
For instance, the addition of heat raises the temperature of a solid; the amount of heat absorbed depends on the heat capacity of the solid (q = mcsolidΔT). According to thermochemistry, the relation between the amount of heat absorbed or released by a substance, q, and its...
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Entropy and Solvation02:05

Entropy and Solvation

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The process of surrounding a solute with solvent is called solvation. It involves evenly distributing the solute within the solvent. The rule of thumb for determining a solvent for a given compound is that like dissolves like. A good solvent has molecular characteristics similar to those of the compound to be dissolved. For example, polar solutions dissolve polar solutes, and apolar solvents dissolve apolar solutes. A polar solvent is a solvent that has a high dielectric constant (ϵ...
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Physical Properties Affecting Solubility02:19

Physical Properties Affecting Solubility

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Solutions of Gases in Liquids
As for any solution, the solubility of a gas in a liquid is affected by the attractive intermolecular forces between solute and solvent species. Unlike solid and liquid solutes, however, there is no solute-solute intermolecular attraction to overcome when a gaseous solute dissolves in a liquid solvent since the atoms or molecules comprising a gas are far separated and experience negligible interactions. Consequently, solute-solvent interactions are the sole...
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Phase Transitions: Melting and Freezing02:39

Phase Transitions: Melting and Freezing

14.4K
Heating a crystalline solid increases the average energy of its atoms, molecules, or ions, and the solid gets hotter. At some point, the added energy becomes large enough to partially overcome the forces holding the molecules or ions of the solid in their fixed positions, and the solid begins the process of transitioning to the liquid state or melting. At this point, the temperature of the solid stops rising, despite the continual input of heat, and it remains constant until all of the solid is...
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A Microfluidic Approach for the Study of Ice and Clathrate Hydrate Crystallization
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Effects of Temperature on Cs+(H2O)20 Clathrate Structure.

Christiane N Stachl1, Evan R Williams1

  • 1Department of Chemistry, University of California, Berkeley, California 94720-1460, United States.

The Journal of Physical Chemistry Letters
|July 8, 2020
PubMed
Summary

Stable cesium-water clusters (Cs+(H2O)20) convert to less stable structures at higher temperatures. Infrared photodissociation spectroscopy reveals this structural change, offering insights into clathrate stability and entropy.

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Area of Science:

  • Physical Chemistry
  • Spectroscopy
  • Computational Chemistry

Background:

  • Cesium ion-water clusters (Cs+(H2O)20) exhibit exceptional stability due to a clathrate structure formed by three-coordinate water molecules.
  • Understanding the temperature-dependent stability of these clathrate structures is crucial for various chemical and physical processes.

Purpose of the Study:

  • To investigate the stability of Cs+(H2O)20 clathrate structures across a range of temperatures.
  • To elucidate the structural transitions from clathrate to non-clathrate forms as a function of temperature.
  • To explore the role of entropy in the stability of these water-ion clusters.

Main Methods:

  • Infrared photodissociation (IRPD) spectroscopy was employed to analyze the vibrational modes of the water molecules.
  • Spectra were recorded in the free-OH stretching region (approximately 3600-3800 cm-1).
  • Experiments were conducted at ion cell temperatures ranging from 135 K to 355 K.

Main Results:

  • At temperatures of 275 K and below, IRPD spectra showed a single acceptor-acceptor-donor band, characteristic of the stable clathrate structure.
  • Above 275 K, a new, higher-energy acceptor-donor band appeared and increased in intensity, indicating the formation of non-clathrate structures.
  • Comparison with Na+(H2O)20 revealed that non-clathrate structures contain both spectral bands, with stable intensities across the temperature range.

Conclusions:

  • A rapid transition from clathrate to non-clathrate structures occurs with increasing temperature.
  • The clathrate structure of Cs+(H2O)20 persists to some extent even at the highest temperatures studied.
  • These findings provide novel insights into the influence of entropy on the stability of clathrate hydrates.