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Silicates and Silicones: Structure From One Building Block

Inorganic Chemistry · Main Group Silicates and Silicones: Structure From One Building Block Every silicate is built from the same tetrahedron. What varies is how many corners are shared, and that single number determines the structure. BSc & MSc · Inorganic Chemistry · Concept The short answer: A silicate tetrahedron shares between zero and four of its corner oxygens with neighbours. Sharing none gives discrete anions, two gives chains or rings, three gives sheets, and four gives a three-dimensional network. Silicones are synthetic polymers with a silicon–oxygen backbone and organic side groups. The building block Every silicate contains silicon at…

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The Thermodynamics of Mixing

Physical Chemistry · Thermodynamics The Thermodynamics of Mixing Why two liquids mix even when nothing energetic is gained, and what has to be true for them not to. BSc & MSc · Physical Chemistry · Concept The short answer: For an ideal solution the enthalpy of mixing is zero, so mixing is driven entirely by the entropy increase from having more accessible arrangements. Since that entropy term is always positive, ideal liquids always mix. Immiscibility therefore requires a positive enthalpy of mixing large enough to overcome it. The entropy of mixing Mixing increases the number of ways the molecules can…

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Catalytic Cycles: Hydroformylation and the Wacker Process

Inorganic Chemistry · Catalysis Catalytic Cycles: Hydroformylation and the Wacker Process Industrial catalysis assembled from four elementary steps that repeat in different orders. Learn the steps and any cycle becomes readable. BSc & MSc · Inorganic Chemistry · Concept The short answer: Homogeneous catalytic cycles are built from a small set of elementary organometallic steps: oxidative addition, migratory insertion, reductive elimination and ligand substitution. Hydroformylation and the Wacker process are the two standard examples, and each is examined by asking which step does what. The elementary steps Step What changes Oxidation state Electron count Oxidative addition A bond adds across…

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Crystal Defects and Non-Stoichiometry

Inorganic Chemistry · Solid State Crystal Defects and Non-Stoichiometry A perfect crystal would have zero entropy of disorder, which thermodynamics forbids above absolute zero. Defects are not flaws but a requirement. BSc & MSc · Inorganic Chemistry · Concept The short answer: Point defects exist in every real crystal because they increase entropy enough to lower the free energy despite costing enthalpy. Schottky defects remove ion pairs and reduce density; Frenkel defects relocate an ion and leave density unchanged. Non-stoichiometric compounds arise when defects are accompanied by a change in oxidation state. Why defects must exist Defects are thermodynamically required,…

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Osmotic Pressure and the van’t Hoff Factor

Physical Chemistry · Solutions Osmotic Pressure and the van’t Hoff Factor The most sensitive of the colligative properties, and the only one practical for measuring the molar mass of very large molecules. BSc & MSc · Physical Chemistry · Concept The short answer: Osmotic pressure is the pressure that must be applied to stop solvent flowing through a semipermeable membrane into a solution. It is far larger than the other colligative effects at the same concentration, which is why it is the method of choice for polymers and proteins. The van’t Hoff factor corrects for dissociation or association of the…

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Noble Gas Compounds: Why Xenon Reacts and Helium Does Not

Inorganic Chemistry · Main Group Noble Gas Compounds: Why Xenon Reacts and Helium Does Not The elements once believed inert form a well-defined set of compounds, and which ones form is entirely predictable from ionisation energy. BSc & MSc · Inorganic Chemistry · Concept The short answer: Xenon has a low enough ionisation energy to be oxidised by fluorine and oxygen. Its fluorides have structures predicted correctly by VSEPR once the lone pairs are counted, and the fluorides hydrolyse to oxides and oxofluorides. Helium and neon do not react, because their ionisation energies are far too high. Why xenon and…

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Ionic Conductance, Kohlrausch’s Law and Transport Numbers

Physical Chemistry · Electrochemistry Ionic Conductance, Kohlrausch’s Law and Transport Numbers Conductance measurements answer questions that look inaccessible — the degree of dissociation of a weak acid, and the solubility of a nearly insoluble salt. BSc & MSc · Physical Chemistry · Concept The short answer: Molar conductivity rises as a solution is diluted, but for different reasons in strong and weak electrolytes. Kohlrausch’s law of independent migration lets the limiting conductivity of a weak electrolyte be constructed from ionic values, which then gives its degree of dissociation and dissociation constant. The quantities Conductivity is conductance per unit dimension of…

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Mass Spectrometry: Reading Fragmentation Patterns

Organic Chemistry · Spectroscopy Mass Spectrometry: Reading Fragmentation Patterns The molecular ion gives the mass. The fragments give the structure, and they fragment in predictable ways. BSc & MSc · Spectroscopy · Method The short answer: The molecular ion peak gives the molecular mass, and isotope peaks reveal certain elements immediately. Fragmentation follows rules based on which cation is most stable, so the losses observed identify the groups present. The nitrogen rule links an odd molecular mass to an odd number of nitrogens. What the spectrum shows The sample is ionised, and the resulting ions are separated by mass-to-charge ratio….

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Ideal and Non-Ideal Solutions: Raoult, Henry and Azeotropes

Physical Chemistry · Solutions Ideal and Non-Ideal Solutions: Raoult, Henry and Azeotropes Deviations from ideality are not an inconvenience — they are the reason azeotropes exist, and the sign of the deviation predicts which kind forms. BSc & MSc · Physical Chemistry · Concept The short answer: An ideal solution obeys Raoult’s law across the whole composition range, which requires the interactions between unlike molecules to match those between like ones. Where unlike interactions are weaker, the solution shows positive deviation and can form a minimum boiling azeotrope; where stronger, negative deviation and a maximum boiling azeotrope. Raoult’s law and…

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The Jahn–Teller Effect: Why Some Complexes Distort

Inorganic Chemistry · Structure The Jahn–Teller Effect: Why Some Complexes Distort A degenerate electronic state is unstable against distortion. Knowing which configurations are degenerate tells you immediately which complexes distort and how strongly. BSc & MSc · Inorganic Chemistry · Concept The short answer: A non-linear molecule in a degenerate electronic state will distort to remove that degeneracy, because doing so lowers the energy. In octahedral complexes the effect is strong for unevenly occupied eg orbitals and weak for uneven t2g occupation, because eg orbitals point directly at ligands. The statement Any non-linear molecule in a degenerate electronic state is…

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