H3 Chemistry Definitions
H3 Chemistry 9813 definitions for spectroscopy, molecular stereochemistry and organic mechanisms, with H2 foundations.
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A reference for H3 Chemistry (9813): the additional spectroscopy, stereochemistry and mechanism content, followed by the H2 foundations examined with H3. The three-topic H3 roadmap keeps its own course progress; the H2 material remains part of the examined foundation.
Molecular orbitals and optical spectra
| Term | Meaning | Remember |
|---|---|---|
| Molecular orbital | Orbital describing an electron distribution over a molecule rather than an isolated atom. | LCAO is a model for constructing MOs from atomic orbitals. |
| Bonding / antibonding MO | Orbital whose occupancy stabilises / destabilises bonding relative to the separated atoms. | Antibonding orbitals have a node between the relevant nuclei and are labelled with an asterisk. |
| Nonbonding MO | Orbital whose occupancy has little effect on the bond in the model. | Distinguish from an empty antibonding orbital. |
| HOMO / LUMO | Highest occupied / lowest unoccupied molecular orbital. | The energy gap helps interpret an accessible electronic transition. |
| Conjugation | Delocalisation arising from overlap of adjacent suitable p orbitals. | Extended conjugation commonly reduces the electronic energy gap. |
| Chromophore | Part of a molecule responsible for absorption in a specified spectral region. | Identify the orbitals and transition; a coloured compound must absorb visible light. |
| Absorbance | Base-10 logarithm of incident intensity divided by transmitted intensity. | No unit; not the same quantity as absorbed intensity or transmittance. |
| Molar absorption coefficient | Proportionality constant relating absorbance to concentration and optical path length at a specified wavelength. | Units must match the chosen concentration and path length. |
| Stretching / bending vibration | Vibration changing bond length / bond angle. | IR absorption requires a change in molecular dipole moment during the vibration. |
| Wavenumber | Reciprocal of wavelength. | Often cm⁻¹ on an IR axis; larger wavenumber corresponds to higher photon energy. |
NMR and mass spectrometry
| Term | Meaning | Remember |
|---|---|---|
| Chemical shift | Resonance position relative to a reference, expressed on the dimensionless ppm scale. | TMS defines 0 ppm in the usual proton NMR convention. |
| Shielding / deshielding | Reduction / relative increase of the effective magnetic field at a nucleus due to its electronic environment. | Deshielded protons generally resonate at larger chemical shift. |
| Equivalent protons | Protons having the same chemical environment on the NMR timescale. | Count environments, not simply hydrogen atoms or carbon atoms. |
| Integration | Measurement of the area under an NMR signal or multiplet. | Proportional to the number of contributing nuclei under suitable conditions. |
| Spin–spin splitting | Splitting of a resonance by coupling to nearby nonequivalent nuclei. | Equivalent neighbouring protons give the familiar first-order n + 1 pattern. |
| Labile proton | Proton that can exchange readily, such as many O–H or N–H protons. | D₂O exchange can remove its proton signal. |
| Anisotropic effect | Direction-dependent local magnetic-field effect of an electron distribution. | Helps explain why aromatic and alkene proton shifts differ. |
| Molecular ion | Ion formed by removing an electron from a molecule without breaking it apart. | In electron-impact spectra it is often a radical cation. |
| Fragment ion | Charged species formed by fragmentation of an ion. | A neutral fragment is not detected as an ion peak. |
| Mass-to-charge ratio, m/z | Ion mass divided by its charge number on the mass-spectral scale. | A singly charged molecular ion often gives its nominal molecular mass. |
| Base peak | Most intense peak in a mass spectrum, assigned relative intensity 100%. | It need not be the molecular-ion peak. |
| Isotope pattern | Related peaks arising from different isotope compositions of the same ion. | One chlorine commonly gives M:M+2 near 3:1; one bromine near 1:1. |
Stereochemistry
| Term | Meaning | Remember |
|---|---|---|
| Conformation | Spatial arrangement that can change through rotation about single bonds without breaking them. | Rotational barriers can make some conformations more populated. |
| Configuration | Stereochemical arrangement that cannot be changed by ordinary single-bond rotation. | R/S and E/Z describe configurations. |
| Newman projection | View along a specified bond, showing front and rear atom substituents. | State which atom is viewed from the front. |
| Enantiomers | Non-superimposable mirror-image stereoisomers. | Opposite optical rotations under the same conditions. |
| Diastereomers | Stereoisomers that are not mirror images of each other. | Often have different ordinary physical properties. |
| Chiral / achiral | Not superimposable / superimposable on the mirror image. | A molecule with stereocentres can still be achiral if symmetry makes it superimposable. |
| Racemic mixture | Equal amounts of two enantiomers. | No net optical rotation because their rotations cancel. |
| Meso compound | Achiral compound containing stereocentres, with internal symmetry causing mirror-image superimposability. | It is one compound, not a racemic mixture. |
| R / S | Configuration labels from Cahn–Ingold–Prelog priorities around a stereocentre. | With lowest priority pointing away, clockwise 1→2→3 is R; anticlockwise is S. |
| E / Z | Alkene configuration with higher-priority substituents opposite / together. | Assign priorities separately at each double-bond carbon. |
| Optical activity | Ability to rotate the plane of plane-polarised light. | Sign of rotation cannot be inferred from R/S alone. |
Mechanisms and selectivity
| Term | Meaning | Remember |
|---|---|---|
| Hammond postulate | A transition state resembles the adjacent stable species closest to it in energy. | Use the energy profile; do not apply it as an unsupported structural slogan. |
| Transition state | High-energy configuration at a reaction-coordinate maximum. | Not a stable intermediate that can be isolated. |
| Intermediate | Species at a local energy minimum between elementary steps. | Has a finite lifetime; distinguish from a transition state. |
| SN1 / SN2 | Substitution through a unimolecular rate-controlling ionisation / a bimolecular concerted displacement. | Rate law and stereochemistry supply evidence for the model. |
| Ion pair | Closely associated oppositely charged ions after ionisation. | Can bias SN1 stereochemistry, so a perfectly 50:50 product mixture is not guaranteed. |
| Leaving group | Atom or group that departs with the bonding electron pair in heterolytic cleavage. | Leaving-group stability affects reaction rate. |
| E1 / E2 | Elimination through stepwise unimolecular ionisation / a concerted bimolecular step. | E2 requires a suitable orientation of breaking bonds. |
| Syn / anti elimination | Eliminating groups leave from the same / opposite side in the relevant geometry. | Anti-periplanar geometry is commonly favoured in E2. |
| Regioselectivity | Preference for reaction at one of several possible positions. | Different positions give constitutional product alternatives. |
| Stereoselectivity | Preferential formation of one stereoisomer over another. | Distinguish from a stereospecific pathway fixed by starting configuration. |
| Zaitsev / Hofmann product | More substituted / less substituted alkene in the usual elimination comparison. | Conditions, base and substrate control the preference; these are not exception-free rules. |
Test the distinction
A pure enantiomer and a racemic mixture contain chiral molecules. The mixture is optically inactive because equal and opposite rotations cancel. An achiral meso compound is inactive for a different reason: its own mirror image is superimposable. Use structure and sample composition together.
H2 foundations examined with H3
Open the H2 definitions
Atoms, orbitals and bonding
| Term | Meaning | Remember |
|---|---|---|
| Isotope | An atom of the same element as another, with a different neutron number. | Proton number fixes the element; nucleon number can differ. |
| Atomic orbital | A region described by a one-electron wavefunction, associated with a probability distribution for an electron in an atom. | An orbital is not a circular path; it holds at most two electrons with opposite spins. |
| First ionisation energy | Energy required to remove one mole of electrons from one mole of isolated gaseous atoms to form one mole of gaseous singly positive ions. | X(g) → X + (g) + e⁻; kJ/mol; the gaseous condition matters. |
| Electronegativity | Ability of an atom in a bond to attract the bonding electrons towards itself. | A comparison within bonding; different from ionisation energy. |
| Ionic bond | Electrostatic attraction between oppositely charged ions. | Acts throughout an extended lattice. |
| Covalent bond | Electrostatic attraction between a shared electron pair and the nuclei of bonded atoms. | A bond may be polar even when the whole molecule is non-polar. |
| Dative covalent bond | Covalent bond whose shared pair is supplied by one atom. | Once formed, it is not a different kind of attraction. |
| Metallic bond | Attraction between positive metal ions and delocalised electrons. | Delocalisation helps explain conduction and malleability. |
| Sigma bond | Covalent bond formed by head-on orbital overlap along the internuclear axis. | A carbon–carbon single bond is a sigma bond. |
| Pi bond | Covalent bond formed by sideways overlap, with electron density on opposite sides of the internuclear axis. | A double bond contains one sigma and one pi bond. |
| Hydrogen bond | Attraction between hydrogen bonded to N, O or F and a lone pair on N, O or F in the school model. | Stronger than many other intermolecular attractions, but not an O–H covalent bond. |
| Permanent dipole | Separation of partial positive and negative charge in a molecule. | Molecular shape determines whether bond dipoles cancel. |
| Instantaneous dipole–induced dipole attraction | Attraction arising when a fluctuating electron distribution induces a dipole in a neighbouring particle. | Present in all atoms and molecules; strength depends on polarisation and contact. |
| Bond energy | Energy required to break one mole of a specified covalent bond in gaseous species. | Bond breaking is endothermic; average bond energies give estimates. |
| Bond length | Equilibrium distance between the nuclei of two bonded atoms. | Compare the specified bonds rather than atomic radii alone. |
Moles, reacting quantities and analysis
| Term | Meaning | Remember |
|---|---|---|
| Mole | Amount containing exactly 6.02214076 × 10²³ specified entities. | State whether the entities are atoms, molecules, ions or electrons. |
| Relative isotopic mass | Mass of an atom of a particular isotope compared with one twelfth of the mass of a carbon-12 atom. | A ratio, with no unit. |
| Relative atomic mass | Weighted mean mass of atoms of an element compared with one twelfth of the mass of a carbon-12 atom. | Includes isotope abundances. |
| Relative molecular / formula mass | Sum of relative atomic masses in a molecule / formula unit. | No unit; distinguish from molar mass in g/mol. |
| Empirical formula | Simplest whole-number ratio of atoms of each element in a compound. | Derived from mole ratios, not mass ratios directly. |
| Molecular formula | Actual number of atoms of each element in a molecule. | A whole-number multiple of the empirical formula. |
| Molar concentration | Amount of solute per unit volume of solution. | Common unit mol/dm³; use solution volume, not solvent volume. |
| Limiting reactant | Reactant exhausted first according to the balanced reacting ratio. | Compare moles divided by their coefficients, not masses directly. |
| Oxidation | Loss of electrons or increase in oxidation number. | Oxidising agents are themselves reduced. |
| Reduction | Gain of electrons or decrease in oxidation number. | Reducing agents are themselves oxidised. |
| Oxidation number | Formal charge assigned to an atom using electron-allocation rules. | Not necessarily the actual charge on that atom. |
| Endpoint | Experimentally observed signal used to stop a titration. | Should lie close to, but is conceptually different from, the equivalence point. |
| Equivalence point | Point at which titrant and analyte have reacted in their stoichiometric ratio. | Does not necessarily have pH 7. |
Enthalpy and energy
| Term | Meaning | Remember |
|---|---|---|
| Enthalpy change of reaction | Heat change for a reaction at constant pressure, for the quantities specified by its equation. | State the reaction equation and molar basis. |
| Standard conditions | Specified reference conditions: standard pressure 100 kPa, stated temperature and species in their standard states. | Standard does not automatically fix the temperature at 298 K; it must be stated. |
| Standard enthalpy change of formation | Enthalpy change when one mole of a substance forms from its elements in their standard states under standard conditions. | Fractional coefficients are allowed to form exactly one mole. |
| Standard enthalpy change of combustion | Enthalpy change when one mole of a substance burns completely in oxygen under standard conditions, with all substances in their standard states. | Specify the product states, especially water. |
| Standard enthalpy change of neutralisation | Enthalpy change when acid and base react to form one mole of water under standard conditions. | The one-mole basis is water, not always acid. |
| Lattice energy | Enthalpy change when one mole of an ionic solid forms from its separated gaseous ions. | Formation convention: negative; a lattice dissociation value uses the opposite sign. |
| Hess’s law | Reaction enthalpy depends only on initial and final states, not the route between them. | Reversing an equation reverses its enthalpy sign. |
| Exothermic / endothermic | A process releasing heat to / absorbing heat from its surroundings. | Negative / positive Δ H; temperature change depends on which part is measured. |
| Activation energy | Minimum energy needed by reacting particles for a successful reaction along a specified pathway. | A catalyst changes the pathway; it does not change reaction enthalpy. |
Rates and equilibrium
| Term | Meaning | Remember |
|---|---|---|
| Rate of reaction | Change in concentration of a specified reactant or product per unit time, with the sign or stoichiometric convention stated. | Product formation and reactant disappearance can have different numerical rates. |
| Rate equation | Experimentally determined relationship between rate and reactant concentrations at fixed temperature. | r = k[A]^m[B]ⁿ; powers need not equal overall equation coefficients. |
| Order with respect to a reactant | Power of that reactant’s concentration in the rate equation. | Overall order is the sum of the powers. |
| Rate constant | Proportionality constant in a rate equation at a specified temperature. | Units depend on overall order; temperature and catalyst affect its value. |
| Half-life | Time for the concentration of a specified reactant to fall to half its initial value. | Successive half-lives are constant for a first-order reaction. |
| Catalyst | Substance that increases rate through an alternative pathway and is regenerated overall. | It changes neither the equilibrium constant nor the equilibrium composition at fixed temperature. |
| Homogeneous / heterogeneous catalyst | Catalyst in the same phase as / a different phase from the reactants. | Surface adsorption matters in heterogeneous catalysis. |
| Enzyme | Biological catalyst, usually a protein, with a specific active site. | Temperature and pH can change its activity. |
| Dynamic equilibrium | State in a closed system where forward and reverse rates are equal and macroscopic composition stays constant. | Reactant and product concentrations need not be equal. |
| Le Chatelier’s principle | When an equilibrium system is disturbed, its response tends to oppose the imposed change. | A catalyst speeds approach to equilibrium without shifting it. |
| Equilibrium constant | Value of the equilibrium composition expression for a specified reaction at a specified temperature. | Use equilibrium concentrations or partial pressures; changing temperature can change the constant. |
Acids, bases and buffers
| Term | Meaning | Remember |
|---|---|---|
| Arrhenius acid / base | Substance increasing hydrogen-ion / hydroxide-ion concentration in aqueous solution. | This model is limited to aqueous systems. |
| Brønsted–Lowry acid / base | Proton donor / proton acceptor. | Identify the species that actually transfers or accepts the proton. |
| Conjugate acid–base pair | Two species differing by one proton. | Their charges differ by one unit. |
| Strong / weak acid | Acid that ionises essentially completely / partially in water under the stated conditions. | Strength and concentration describe different things. |
| Strong / weak base | Base reacting essentially completely / partially with water to generate hydroxide ions, or a hydroxide that dissociates essentially completely / partially. | Compare like species and the appropriate equilibrium. |
| pH | Negative base-10 logarithm of the numerical hydrogen-ion concentration in mol/dm³ in the school concentration model. | pH measures acidity; it is not a direct measure of total acid concentration. |
| Acid dissociation constant, Kₐ | Equilibrium constant for an acid transferring a proton to water. | For HA, Kₐ = [H⁺][A⁻]/[HA]; depends on temperature. |
| Base dissociation constant, K_b | Equilibrium constant for a base reacting with water to produce its conjugate acid and hydroxide ions. | For B, K_b = [BH⁺][OH⁻]/[B]. |
| Ionic product of water, K_w | Product of hydrogen-ion and hydroxide-ion concentrations in the school model at a specified temperature. | Neutrality means equal ion concentrations, not pH 7 at every temperature. |
| Buffer | Solution that resists changes in pH when small amounts of acid or alkali are added. | Contains appreciable amounts of a weak acid/base and its conjugate partner; capacity is finite. |
| Acid–base indicator | Weak acid/base whose conjugate forms have different colours. | Choose its transition range within the steep part of the titration curve. |
| Amphoteric substance | Substance that can react as both an acid and a base. | Identify its role in each particular reaction. |
Organic chemistry and polymers
| Term | Meaning | Remember |
|---|---|---|
| Functional group | Atom or group responsible for characteristic reactions of an organic compound. | The same molecule can have more than one functional group. |
| Homologous series | Family with the same functional group and general formula, similar chemical reactions and a gradation of physical properties. | Successive members differ by CH₂. |
| Structural isomers | Compounds with the same molecular formula but different connectivity. | Atoms are joined in different orders. |
| Stereoisomers | Compounds with the same connectivity but different spatial arrangements. | Compare with structural isomers. |
| Cis–trans isomerism | Stereoisomerism arising from restricted rotation, with groups on the same or opposite sides of a reference plane. | Each alkene carbon needs two different substituents for alkene cis–trans isomerism. |
| Addition / substitution | Reaction adding groups across a multiple bond / replacing an atom or group. | Distinguish product connectivity, not just reactant names. |
| Elimination | Reaction removing atoms or groups to create a multiple bond. | Often competes with substitution for a suitable substrate. |
| Condensation | Reaction joining molecules with elimination of a small molecule. | Ester and amide formation are examples. |
| Hydrolysis | Bond cleavage involving reaction with water. | Acidic or alkaline conditions can give different final species. |
| Addition polymerisation | Joining unsaturated monomers without eliminating small molecules. | The repeat unit is not the unchanged alkene molecule. |
| Condensation polymerisation | Joining suitable monomers with loss of small molecules. | A difunctional monomer can form a chain. |
| Denaturation | Loss of a protein’s functional three-dimensional structure. | Does not normally mean hydrolysis of its primary peptide sequence. |
Further H2 terms
| Term | Meaning | Remember |
|---|---|---|
| Ideal gas | Model with negligible particle volume and negligible intermolecular forces except during elastic collisions. | Best approached at low pressure and high temperature. |
| Partial pressure | Pressure a gas component would exert alone in the mixture’s total volume at the same temperature. | pᵢ = xᵢ pₜₒₜₐₗ for an ideal mixture. |
| Entropy | Thermodynamic quantity related to the number of microscopic arrangements accessible to a system. | Unit J/(mol K) for molar entropy; particle number, phase and energy distribution matter. |
| Gibbs free-energy change | Thermodynamic change Δ G = Δ H-TΔ S at a stated temperature. | Negative Δ G favours forward change at constant temperature and pressure; it does not imply a fast reaction. |
| Standard enthalpy change of atomisation | Enthalpy change forming one mole of gaseous atoms from an element in its standard state. | Molar basis is atoms, not necessarily one mole of the element’s molecules. |
| Standard enthalpy change of hydration | Enthalpy change when one mole of gaseous ions becomes hydrated aqueous ions under standard conditions. | Usually exothermic; stronger charge density strengthens hydration. |
| Standard enthalpy change of solution | Enthalpy change dissolving one mole of a substance in sufficient solvent under standard conditions. | Combine the specified lattice and hydration conventions consistently. |
| Electron affinity | Enthalpy change when one mole of gaseous atoms gains one mole of electrons to form gaseous anions. | First and successive electron affinities need not have the same sign. |
| Rate-determining step | Slow step that controls the rate in an appropriate multi-step mechanism. | A proposed mechanism must also reproduce the observed rate law. |
| Lewis acid / base | Electron-pair acceptor / electron-pair donor. | Forms an adduct through a dative bond; no proton is required. |
| pKₐ | Negative base-10 logarithm of the numerical Kₐ value in the stated concentration convention. | Lower pKₐ corresponds to larger Kₐ and stronger acid. |
| Solubility product, Kₛₚ | Equilibrium product of ion concentrations, raised to stoichiometric powers, for a saturated solution in contact with its solid. | Pure solid is omitted; solubility is not generally equal to Kₛₚ. |
| Common-ion effect | Suppression of an ionisation or dissolution equilibrium by adding a species that supplies an ion already present. | Account for the added ion before evaluating equilibrium concentrations. |
| Standard electrode potential | Electrode potential of a specified half-cell relative to the standard hydrogen electrode under standard conditions. | Reduction potentials are tabulated; reverse the chemistry when an electrode is oxidised. |
| Standard hydrogen electrode | Reference half-cell of hydrogen gas at standard pressure, hydrogen-ion concentration 1 mol/dm³ and a platinum electrode, at stated temperature. | Assigned potential 0 V. |
| Electrolysis | Chemical change at electrodes driven by an external electric current. | Oxidation occurs at the anode; reduction at the cathode. |
| Faraday constant | Charge per mole of electrons. | Approximately 9.65 × 10⁴ C/mol. |
| Transition element | Element whose atom or at least one of its ions has an incomplete d subshell. | Zinc is not a transition element under this definition. |
| Ligand | Species that donates an electron pair to a central metal atom or ion to form a coordinate bond. | A multidentate ligand can donate through several donor atoms. |
| Coordination number | Number of donor atoms directly bonded to the central metal atom or ion. | Count donor atoms, not merely ligand molecules. |
| Complex ion | Charged species containing a central metal atom/ion coordinated to ligands. | Charge belongs to the whole species, including the ligands. |
| Ligand exchange | Replacement of one ligand by another at a central metal. | Need not change metal oxidation number. |
| Electrophile | Species that accepts an electron pair to form a covalent bond. | Curly arrows point towards its receiving atom or bond. |
| Nucleophile | Species that donates an electron pair to form a covalent bond. | May be negatively charged or neutral with a lone pair. |
| Free radical | Species with an unpaired electron. | Use single-headed arrows for single-electron movement. |
| Heterolytic / homolytic fission | Bond cleavage giving both bonding electrons to one atom / one electron to each atom. | Produces ions / radicals in the simple models. |
| Chiral molecule | Molecule not superimposable on its mirror image. | One tetrahedral carbon with four different groups is a common cause, not a universal test. |
| Enantiomers | Non-superimposable mirror-image stereoisomers. | A pure enantiomer rotates plane-polarised light; a racemic mixture has no net rotation. |
| Racemic mixture | Equal amounts of a pair of enantiomers. | Optical rotations cancel, but the mixture is not a single achiral molecule. |
| Amino acid | Organic compound containing amino and carboxyl functional groups. | Speciation depends on pH; a zwitterion has both positive and negative charges. |
| Zwitterion | Species with positive and negative charges at different sites and zero overall charge. | It is not a neutral structure without formal charges. |
| Peptide bond | Amide linkage joining amino-acid residues. | Condensation forms it; hydrolysis breaks it. |
H3 stopping point
Use the supplied Data Booklet for characteristic IR absorptions. Quantitative LCAO and mathematical steady-state treatment are not required. The NMR energy discussion is qualitative; Fischer projections, fac/mer identification and solvent effects in the SN1/SN2 comparison are outside the specified additional scope.
Return to the H3 course hub for spectra, structures and mechanism reasoning.