H3 Chemistry Definitions

H3 Chemistry 9813 definitions for spectroscopy, molecular stereochemistry and organic mechanisms, with H2 foundations.

  • GCE A-Level H3 Chemistry 9813-2027
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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.

Course hub · Formula list

Molecular orbitals and optical spectra

TermMeaningRemember
Molecular orbitalOrbital describing an electron distribution over a molecule rather than an isolated atom.LCAO is a model for constructing MOs from atomic orbitals.
Bonding / antibonding MOOrbital 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 MOOrbital whose occupancy has little effect on the bond in the model.Distinguish from an empty antibonding orbital.
HOMO / LUMOHighest occupied / lowest unoccupied molecular orbital.The energy gap helps interpret an accessible electronic transition.
ConjugationDelocalisation arising from overlap of adjacent suitable p orbitals.Extended conjugation commonly reduces the electronic energy gap.
ChromophorePart of a molecule responsible for absorption in a specified spectral region.Identify the orbitals and transition; a coloured compound must absorb visible light.
AbsorbanceBase-10 logarithm of incident intensity divided by transmitted intensity.No unit; not the same quantity as absorbed intensity or transmittance.
Molar absorption coefficientProportionality constant relating absorbance to concentration and optical path length at a specified wavelength.Units must match the chosen concentration and path length.
Stretching / bending vibrationVibration changing bond length / bond angle.IR absorption requires a change in molecular dipole moment during the vibration.
WavenumberReciprocal of wavelength.Often cm⁻¹ on an IR axis; larger wavenumber corresponds to higher photon energy.

NMR and mass spectrometry

TermMeaningRemember
Chemical shiftResonance position relative to a reference, expressed on the dimensionless ppm scale.TMS defines 0 ppm in the usual proton NMR convention.
Shielding / deshieldingReduction / relative increase of the effective magnetic field at a nucleus due to its electronic environment.Deshielded protons generally resonate at larger chemical shift.
Equivalent protonsProtons having the same chemical environment on the NMR timescale.Count environments, not simply hydrogen atoms or carbon atoms.
IntegrationMeasurement of the area under an NMR signal or multiplet.Proportional to the number of contributing nuclei under suitable conditions.
Spin–spin splittingSplitting of a resonance by coupling to nearby nonequivalent nuclei.Equivalent neighbouring protons give the familiar first-order n + 1 pattern.
Labile protonProton that can exchange readily, such as many O–H or N–H protons.D₂O exchange can remove its proton signal.
Anisotropic effectDirection-dependent local magnetic-field effect of an electron distribution.Helps explain why aromatic and alkene proton shifts differ.
Molecular ionIon formed by removing an electron from a molecule without breaking it apart.In electron-impact spectra it is often a radical cation.
Fragment ionCharged species formed by fragmentation of an ion.A neutral fragment is not detected as an ion peak.
Mass-to-charge ratio, m/zIon mass divided by its charge number on the mass-spectral scale.A singly charged molecular ion often gives its nominal molecular mass.
Base peakMost intense peak in a mass spectrum, assigned relative intensity 100%.It need not be the molecular-ion peak.
Isotope patternRelated 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

TermMeaningRemember
ConformationSpatial arrangement that can change through rotation about single bonds without breaking them.Rotational barriers can make some conformations more populated.
ConfigurationStereochemical arrangement that cannot be changed by ordinary single-bond rotation.R/S and E/Z describe configurations.
Newman projectionView along a specified bond, showing front and rear atom substituents.State which atom is viewed from the front.
EnantiomersNon-superimposable mirror-image stereoisomers.Opposite optical rotations under the same conditions.
DiastereomersStereoisomers that are not mirror images of each other.Often have different ordinary physical properties.
Chiral / achiralNot superimposable / superimposable on the mirror image.A molecule with stereocentres can still be achiral if symmetry makes it superimposable.
Racemic mixtureEqual amounts of two enantiomers.No net optical rotation because their rotations cancel.
Meso compoundAchiral compound containing stereocentres, with internal symmetry causing mirror-image superimposability.It is one compound, not a racemic mixture.
R / SConfiguration labels from Cahn–Ingold–Prelog priorities around a stereocentre.With lowest priority pointing away, clockwise 1→2→3 is R; anticlockwise is S.
E / ZAlkene configuration with higher-priority substituents opposite / together.Assign priorities separately at each double-bond carbon.
Optical activityAbility to rotate the plane of plane-polarised light.Sign of rotation cannot be inferred from R/S alone.

Mechanisms and selectivity

TermMeaningRemember
Hammond postulateA 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 stateHigh-energy configuration at a reaction-coordinate maximum.Not a stable intermediate that can be isolated.
IntermediateSpecies at a local energy minimum between elementary steps.Has a finite lifetime; distinguish from a transition state.
SN1 / SN2Substitution through a unimolecular rate-controlling ionisation / a bimolecular concerted displacement.Rate law and stereochemistry supply evidence for the model.
Ion pairClosely associated oppositely charged ions after ionisation.Can bias SN1 stereochemistry, so a perfectly 50:50 product mixture is not guaranteed.
Leaving groupAtom or group that departs with the bonding electron pair in heterolytic cleavage.Leaving-group stability affects reaction rate.
E1 / E2Elimination through stepwise unimolecular ionisation / a concerted bimolecular step.E2 requires a suitable orientation of breaking bonds.
Syn / anti eliminationEliminating groups leave from the same / opposite side in the relevant geometry.Anti-periplanar geometry is commonly favoured in E2.
RegioselectivityPreference for reaction at one of several possible positions.Different positions give constitutional product alternatives.
StereoselectivityPreferential formation of one stereoisomer over another.Distinguish from a stereospecific pathway fixed by starting configuration.
Zaitsev / Hofmann productMore 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

TermMeaningRemember
IsotopeAn atom of the same element as another, with a different neutron number.Proton number fixes the element; nucleon number can differ.
Atomic orbitalA 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 energyEnergy 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.
ElectronegativityAbility of an atom in a bond to attract the bonding electrons towards itself.A comparison within bonding; different from ionisation energy.
Ionic bondElectrostatic attraction between oppositely charged ions.Acts throughout an extended lattice.
Covalent bondElectrostatic 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 bondCovalent bond whose shared pair is supplied by one atom.Once formed, it is not a different kind of attraction.
Metallic bondAttraction between positive metal ions and delocalised electrons.Delocalisation helps explain conduction and malleability.
Sigma bondCovalent bond formed by head-on orbital overlap along the internuclear axis.A carbon–carbon single bond is a sigma bond.
Pi bondCovalent 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 bondAttraction 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 dipoleSeparation of partial positive and negative charge in a molecule.Molecular shape determines whether bond dipoles cancel.
Instantaneous dipole–induced dipole attractionAttraction 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 energyEnergy required to break one mole of a specified covalent bond in gaseous species.Bond breaking is endothermic; average bond energies give estimates.
Bond lengthEquilibrium distance between the nuclei of two bonded atoms.Compare the specified bonds rather than atomic radii alone.

Moles, reacting quantities and analysis

TermMeaningRemember
MoleAmount containing exactly 6.02214076 × 10²³ specified entities.State whether the entities are atoms, molecules, ions or electrons.
Relative isotopic massMass 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 massWeighted 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 massSum of relative atomic masses in a molecule / formula unit.No unit; distinguish from molar mass in g/mol.
Empirical formulaSimplest whole-number ratio of atoms of each element in a compound.Derived from mole ratios, not mass ratios directly.
Molecular formulaActual number of atoms of each element in a molecule.A whole-number multiple of the empirical formula.
Molar concentrationAmount of solute per unit volume of solution.Common unit mol/dm³; use solution volume, not solvent volume.
Limiting reactantReactant exhausted first according to the balanced reacting ratio.Compare moles divided by their coefficients, not masses directly.
OxidationLoss of electrons or increase in oxidation number.Oxidising agents are themselves reduced.
ReductionGain of electrons or decrease in oxidation number.Reducing agents are themselves oxidised.
Oxidation numberFormal charge assigned to an atom using electron-allocation rules.Not necessarily the actual charge on that atom.
EndpointExperimentally observed signal used to stop a titration.Should lie close to, but is conceptually different from, the equivalence point.
Equivalence pointPoint at which titrant and analyte have reacted in their stoichiometric ratio.Does not necessarily have pH 7.

Enthalpy and energy

TermMeaningRemember
Enthalpy change of reactionHeat change for a reaction at constant pressure, for the quantities specified by its equation.State the reaction equation and molar basis.
Standard conditionsSpecified 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 formationEnthalpy 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 combustionEnthalpy 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 neutralisationEnthalpy 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 energyEnthalpy 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 lawReaction enthalpy depends only on initial and final states, not the route between them.Reversing an equation reverses its enthalpy sign.
Exothermic / endothermicA process releasing heat to / absorbing heat from its surroundings.Negative / positive Δ H; temperature change depends on which part is measured.
Activation energyMinimum 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

TermMeaningRemember
Rate of reactionChange 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 equationExperimentally 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 reactantPower of that reactant’s concentration in the rate equation.Overall order is the sum of the powers.
Rate constantProportionality constant in a rate equation at a specified temperature.Units depend on overall order; temperature and catalyst affect its value.
Half-lifeTime for the concentration of a specified reactant to fall to half its initial value.Successive half-lives are constant for a first-order reaction.
CatalystSubstance 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 catalystCatalyst in the same phase as / a different phase from the reactants.Surface adsorption matters in heterogeneous catalysis.
EnzymeBiological catalyst, usually a protein, with a specific active site.Temperature and pH can change its activity.
Dynamic equilibriumState 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 principleWhen an equilibrium system is disturbed, its response tends to oppose the imposed change.A catalyst speeds approach to equilibrium without shifting it.
Equilibrium constantValue 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

TermMeaningRemember
Arrhenius acid / baseSubstance increasing hydrogen-ion / hydroxide-ion concentration in aqueous solution.This model is limited to aqueous systems.
Brønsted–Lowry acid / baseProton donor / proton acceptor.Identify the species that actually transfers or accepts the proton.
Conjugate acid–base pairTwo species differing by one proton.Their charges differ by one unit.
Strong / weak acidAcid that ionises essentially completely / partially in water under the stated conditions.Strength and concentration describe different things.
Strong / weak baseBase 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.
pHNegative 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, KₐEquilibrium constant for an acid transferring a proton to water.For HA, Kₐ = [H⁺][A⁻]/[HA]; depends on temperature.
Base dissociation constant, K_bEquilibrium 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_wProduct 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.
BufferSolution 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 indicatorWeak acid/base whose conjugate forms have different colours.Choose its transition range within the steep part of the titration curve.
Amphoteric substanceSubstance that can react as both an acid and a base.Identify its role in each particular reaction.

Organic chemistry and polymers

TermMeaningRemember
Functional groupAtom or group responsible for characteristic reactions of an organic compound.The same molecule can have more than one functional group.
Homologous seriesFamily with the same functional group and general formula, similar chemical reactions and a gradation of physical properties.Successive members differ by CH₂.
Structural isomersCompounds with the same molecular formula but different connectivity.Atoms are joined in different orders.
StereoisomersCompounds with the same connectivity but different spatial arrangements.Compare with structural isomers.
Cis–trans isomerismStereoisomerism 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 / substitutionReaction adding groups across a multiple bond / replacing an atom or group.Distinguish product connectivity, not just reactant names.
EliminationReaction removing atoms or groups to create a multiple bond.Often competes with substitution for a suitable substrate.
CondensationReaction joining molecules with elimination of a small molecule.Ester and amide formation are examples.
HydrolysisBond cleavage involving reaction with water.Acidic or alkaline conditions can give different final species.
Addition polymerisationJoining unsaturated monomers without eliminating small molecules.The repeat unit is not the unchanged alkene molecule.
Condensation polymerisationJoining suitable monomers with loss of small molecules.A difunctional monomer can form a chain.
DenaturationLoss of a protein’s functional three-dimensional structure.Does not normally mean hydrolysis of its primary peptide sequence.

Further H2 terms

TermMeaningRemember
Ideal gasModel with negligible particle volume and negligible intermolecular forces except during elastic collisions.Best approached at low pressure and high temperature.
Partial pressurePressure a gas component would exert alone in the mixture’s total volume at the same temperature.pᵢ = xᵢ pₜₒₜₐₗ for an ideal mixture.
EntropyThermodynamic 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 changeThermodynamic 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 atomisationEnthalpy 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 hydrationEnthalpy 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 solutionEnthalpy change dissolving one mole of a substance in sufficient solvent under standard conditions.Combine the specified lattice and hydration conventions consistently.
Electron affinityEnthalpy 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 stepSlow step that controls the rate in an appropriate multi-step mechanism.A proposed mechanism must also reproduce the observed rate law.
Lewis acid / baseElectron-pair acceptor / electron-pair donor.Forms an adduct through a dative bond; no proton is required.
pKₐNegative base-10 logarithm of the numerical Kₐ value in the stated concentration convention.Lower pKₐ corresponds to larger Kₐ and stronger acid.
Solubility product, KₛₚEquilibrium 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 effectSuppression 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 potentialElectrode 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 electrodeReference 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.
ElectrolysisChemical change at electrodes driven by an external electric current.Oxidation occurs at the anode; reduction at the cathode.
Faraday constantCharge per mole of electrons.Approximately 9.65 × 10⁴ C/mol.
Transition elementElement whose atom or at least one of its ions has an incomplete d subshell.Zinc is not a transition element under this definition.
LigandSpecies 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 numberNumber of donor atoms directly bonded to the central metal atom or ion.Count donor atoms, not merely ligand molecules.
Complex ionCharged species containing a central metal atom/ion coordinated to ligands.Charge belongs to the whole species, including the ligands.
Ligand exchangeReplacement of one ligand by another at a central metal.Need not change metal oxidation number.
ElectrophileSpecies that accepts an electron pair to form a covalent bond.Curly arrows point towards its receiving atom or bond.
NucleophileSpecies that donates an electron pair to form a covalent bond.May be negatively charged or neutral with a lone pair.
Free radicalSpecies with an unpaired electron.Use single-headed arrows for single-electron movement.
Heterolytic / homolytic fissionBond cleavage giving both bonding electrons to one atom / one electron to each atom.Produces ions / radicals in the simple models.
Chiral moleculeMolecule not superimposable on its mirror image.One tetrahedral carbon with four different groups is a common cause, not a universal test.
EnantiomersNon-superimposable mirror-image stereoisomers.A pure enantiomer rotates plane-polarised light; a racemic mixture has no net rotation.
Racemic mixtureEqual amounts of a pair of enantiomers.Optical rotations cancel, but the mixture is not a single achiral molecule.
Amino acidOrganic compound containing amino and carboxyl functional groups.Speciation depends on pH; a zwitterion has both positive and negative charges.
ZwitterionSpecies with positive and negative charges at different sites and zero overall charge.It is not a neutral structure without formal charges.
Peptide bondAmide 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.