Structure and Properties of Crystals + Allotropes of Carbon

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crystalline solids

Atoms, ions, or molecules that are arranged in a regular repeating pattern is called a crystal lattice. Crystals can be classified as: Ionic solids, Molecular solids, Metallic solids, or Covalent Network solids

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ionic crystals

Structural Particles: Alternating cations (+ve) and anions (-ve)

Intramolecular Force: Ionic bonds (strong, directional)

Intermolecular Force: ION-ION electrostatic force

  • Hardness: Very hard, resists scratching and denting

  • Melting Point: Moderate to very high (~1000°C)

  • Electrical Conductivity: NO as solid; YES when aqueous and molten

  • Solubility: NO in oil; MANY in water → mobbed

  • Brittleness: Very brittle, easily broken apart (like charges come into contact, repel and break apart)

<p><strong>Structural Particles:</strong> Alternating cations (+ve) and anions (-ve)</p><p><strong>Intramolecular Force:</strong> Ionic bonds (strong, <u>directional</u>)</p><p><strong>Intermolecular Force:</strong> ION-ION electrostatic force</p><ul><li><p><u>Hardness</u>: Very hard, resists scratching and denting</p></li><li><p><u>Melting Point</u>: Moderate to very high (~1000°C)</p></li><li><p><u>Electrical Conductivity</u>: NO as solid; YES when aqueous and molten</p></li><li><p><u>Solubility</u>: NO in oil; MANY in water → mobbed</p></li><li><p><u>Brittleness</u>: <strong>Very brittle</strong>, easily broken apart (like charges come into contact, repel and break apart)</p></li></ul>
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metallic crystals

Structural Particles: cation “islands” in a “sea” of delocalised electrons

Intramolecular Force: Metallic bonds (strong, non-directional - acts in all directions)

Intermolecular Force: cation-electron electrostatic force (strong - non-directional)

  • Hardness: Varies from soft to very hard (stronger electrostatic forces and compactness means cations can be held in place more firmly and resist sliding over each other - the more delocalised electrons, the more it resists denting and scratching)

  • Melting Point: Varies from low to high depending on hardness (strong electrostatic forces resist separation)

    Electrical Conductivity: Very good conductors both in solid and liquid state (molten), won’t conduct in water because it won’t dissolve

  • Solubility: Not soluble (overall neutral, so nothing to establish forces with the solvent)

  • Luster: shiny

  • Malleability/Ductility: Malleable (can be hammered) and ductile (can be drawn into wires) → cations slide past each other without coming into contact, hence not breaking the bond

<p><strong>Structural Particles:</strong> cation “islands” in a “sea” of delocalised electrons</p><p><strong>Intramolecular Force:</strong> Metallic bonds (strong, <u>non-directional</u> - acts in all directions)</p><p><strong>Intermolecular Force:</strong> cation-electron electrostatic force (strong - <u>non-directional</u>)</p><ul><li><p><u>Hardness:</u> Varies from soft to very hard (stronger electrostatic forces and compactness means cations can be held in place more firmly and resist sliding over each other - the more delocalised electrons, the more it resists denting and scratching)</p></li><li><p><u>Melting Point:</u> Varies from low to high depending on hardness (strong electrostatic forces resist separation)</p><p><u>Electrical Conductivity:</u> <strong>Very good conductors</strong> both in solid and liquid state (molten), <u><strong><em>won’t conduct in water because it won’t dissolve</em></strong></u></p></li><li><p><u>Solubility:</u> Not soluble (overall neutral, so nothing to establish forces with the solvent)</p></li><li><p>Luster: shiny</p></li><li><p><u>Malleability/Ductility:</u> <strong>Malleable</strong> (can be hammered) and <strong>ductile</strong> (can be drawn into wires) → cations <u><strong>slide</strong></u> past each other without coming into contact, hence not breaking the bond</p></li></ul>
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molecular crystals

** biggest family!

Structural Particles: Atoms, nonpolar molecules, polar molecules, or molecules H-bonded to F, O, N

Intramolecular Force: Polar or nonpolar covalent bonds (strong, directional force within molecules)

Intermolecular Force: London Dispersion < Dipole-Dipole < Hydrogen bonding (weak, somewhat directional)

  • Hardness: Soft (weak intermolecular forces + loose messy lattice mean they are “manipulative” and “squishy”)

  • Melting Point: Low to moderate, can evaporate directly, most melt below 300°C (weak intermolecular forces → more easily separated; MP of nonpolar solids increases with molar mass, MP of polar molecular solids increases with strength of IMF)

  • Electrical Conductivity: POOR, they are insulators (electrons are shared and thus locked in covalent bonds so no ions or electrons can flow → no mobile electrons)

  • Solubility: “Like dissolves Like”; in oil YES if NP; in water YES if P

  • Brittleness: Low flexibility (weak, loose, messy lattice crumbles under pressure)

<p>** biggest family!</p><p><strong>Structural Particles:</strong> Atoms, nonpolar molecules, polar molecules, or molecules H-bonded to F, O, N</p><p><strong>Intramolecular Force:</strong> Polar or nonpolar covalent bonds (strong, <u>directional</u> force within molecules)</p><p><strong>Intermolecular Force:</strong> London Dispersion &lt; Dipole-Dipole &lt; Hydrogen bonding (weak, <u>somewhat directional</u>)</p><ul><li><p><u>Hardness:</u> Soft (weak intermolecular forces + loose messy lattice mean they are “manipulative” and “squishy”)</p></li><li><p><u>Melting Point:</u> Low to moderate, can evaporate directly, most melt below 300°C (weak intermolecular forces → more easily separated; MP of nonpolar solids increases with molar mass, MP of polar molecular solids increases with strength of IMF)</p></li><li><p><u>Electrical Conductivity:</u> POOR, they are <u><strong>insulators</strong></u> (electrons are shared and thus locked in covalent bonds so no ions or electrons can flow → no mobile electrons)</p></li><li><p><u>Solubility:</u> “<strong>Like dissolves Like”</strong>; in oil YES if NP; in water YES if P</p></li><li><p><u>Brittleness:</u> Low flexibility (weak, loose, messy lattice crumbles under pressure)</p></li></ul>
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covalent network crystals

** e.g. sand, quartz, diamond, graphite

Formed by very many atoms or molecules into ONE GIANT MOLECULE

Structural Particles: Atoms (C - diamond, graphite, buckyballs; SiC - moissanite; SiO2 - quartz, sand)

Intramolecular Force: Covalent bonds (strong, directional, interlocking)

Intermolecular Force: London Dispersion forces - in some cases

<p>** e.g. sand, quartz, diamond, graphite</p><p>Formed by <u>very many atoms</u> or <u>molecules</u> into ONE GIANT MOLECULE</p><p><strong>Structural Particles:</strong> Atoms (C - diamond, graphite, buckyballs; SiC - moissanite; SiO2 - quartz, sand)</p><p><strong>Intramolecular Force:</strong> Covalent bonds (strong, <u>directional</u>, interlocking)</p><p><strong>Intermolecular Force:</strong> London Dispersion forces - <em>in some cases</em></p>
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diamond

Covalent Network Crystal, tetrahedral (giant crystal lattice), sp3 hybridization and sigma bonds, no IMFs, VERY HARD (10 Mohs)

  • Hardness: Very hard (strong direction covalent bonds and tetrahedral network resists denting and scratching)

  • Melting Point: Sublimes at 4027°C (strong covalent bonds and tetrahedral network resists separation)

  • Electrical Conductivity: No (electrons shared in bonds so no ions or electrons can flow)

  • Solubility: No (overall neutral, nothing to establish forces with the solvent)

  • Malleability/Ductility: No (complex interlocking network resists flexibility and will break under pressure along fault lines)

<p><strong>Covalent Network Crystal</strong>, tetrahedral (giant crystal lattice), sp3 hybridization and sigma bonds, no IMFs, VERY HARD (10 Mohs)</p><ul><li><p><u>Hardness:</u> Very hard (strong direction covalent bonds and tetrahedral network resists denting and scratching)</p></li><li><p><u>Melting Point:</u> <strong>Sublimes</strong> at 4027°C (strong covalent bonds and tetrahedral network resists separation)</p></li><li><p><u>Electrical Conductivity:</u> <strong>No</strong> (electrons shared in bonds so no ions or electrons can flow)</p></li><li><p><u>Solubility:</u> <strong>No</strong> (overall neutral, nothing to establish forces with the solvent)</p></li><li><p><u>Malleability/Ductility:</u> <strong>No</strong> (complex interlocking network resists flexibility and will break under pressure along fault lines)</p></li></ul>
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graphite

Covalent Network Crystal, trigonal planar (layer-like structure, atoms arranged in flat layers of hexagons, between which is a soup of free-floating, delocalised electrons made up of the spare electrons from sp2 hybridization → pi cloud)

  • Hardness: Soft (2-D sheets/layers of hexagonal rings of carbon atoms slide past each other)

  • Melting Point: Sublimes at 3600°C (London Dispersion forces between sheets resist separation due to size)

  • Electrical Conductivity: YES!! (Pi-cloud has mobile electrons)

  • Solubility: No (overall neutral, nothing to establish forces with the solvent)

  • Malleability/Ductility: FLAKEY (2-D sheets slide past each other; 1-2 Mohs)

<p><strong>Covalent Network Crystal</strong>, trigonal planar (layer-like structure, atoms arranged in flat layers of hexagons, between which is a <u>soup</u> of free-floating, delocalised electrons made up of the spare electrons from sp2 hybridization → pi cloud)</p><ul><li><p><u>Hardness:</u> Soft (2-D sheets/layers of hexagonal rings of carbon atoms slide past each other)</p></li><li><p><u>Melting Point:</u> <strong>Sublimes</strong> at 3600°C (London Dispersion forces between sheets resist separation <u>due to size</u>)</p></li><li><p><u>Electrical Conductivity:</u> <strong>YES!!</strong> (Pi-cloud has mobile electrons)</p></li><li><p><u>Solubility:</u> <strong>No</strong> (overall neutral, nothing to establish forces with the solvent)</p></li><li><p><u>Malleability/Ductility:</u> <strong>FLAKEY</strong> (2-D sheets <u>slide</u> past each other; 1-2 Mohs)</p></li></ul>
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allotrope

Each of two or more different physical forms in which an element can exist; differ in the arrangement of atoms in crystalline solids or in the occurrence of molecules that contain different numbers of atoms.

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catenation

The bonding of atoms of the same element into a series, called a chain.

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10

graphene

Covalent Network Crystal, trigonal planar (thinnest, lightest, strongest, most stretchy material we have ever created, think of it like a single layer extracted from graphite)

  • Hexagonal lattice

  • Hybridization: sp2 hybridization

  • IMFs?: London Dispersion forces

  • Conductivity: Excellent conductor (300x more efficient than copper) due to pi-cloud formed by unhybridized p orbitals

  • Melting Point: Sublimes at 3625°C

  • Solubility: No solubility in water

  • Hardness: Very strong (>10 Mohs)

<p><strong>Covalent Network Crystal</strong>, trigonal planar (thinnest, lightest, strongest, most stretchy material we have ever created, think of it like a single layer extracted from graphite)</p><ul><li><p>Hexagonal lattice</p></li><li><p><u>Hybridization:</u> sp2 hybridization</p></li><li><p><u>IMFs?:</u> London Dispersion forces</p></li><li><p><u>Conductivity</u>: Excellent conductor (300x more efficient than copper) due to pi-cloud formed by unhybridized p orbitals</p></li><li><p><u>Melting Point:</u> Sublimes at 3625°C</p></li><li><p><u>Solubility</u>: No solubility in water</p></li><li><p><u>Hardness:</u> Very strong (&gt;10 Mohs)</p></li></ul>
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11

C60 Fullerene

Molecular Crystal (small, only 60 carbons), trigonal planar (60 C arranged as 10 hexagons and 12 pentagons like a soccer ball)

  • Hybridization: sp2 hybridization

  • IMFs?: Weak London Dispersion forces between C60 molecules

  • Conductivity: Poor conductor compared to graphite; fewer delocalised electrons capable of moving from one molecule to the next

  • Melting Point: Sublimes at 600°C (IMFs are weaker, thus, MP is low)

  • Solubility: No solubility in water

  • Hardness: Very strong (>10 Mohs)

<p><strong>Molecular Crystal</strong> (small, only 60 carbons), trigonal planar (60 C arranged as 10 hexagons and 12 pentagons like a soccer ball)</p><ul><li><p><u>Hybridization</u>: sp2 hybridization</p></li><li><p><u>IMFs?:</u> Weak London Dispersion forces between C60 molecules</p></li><li><p><u>Conductivity:</u> Poor conductor compared to graphite; fewer delocalised electrons capable of moving from one molecule to the next</p></li><li><p><u>Melting Point</u>: Sublimes at 600°C (IMFs are weaker, thus, MP is low)</p></li><li><p><u>Solubility:</u> No solubility in water</p></li><li><p><u>Hardness:</u> Very strong (&gt;10 Mohs)</p></li></ul>
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