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Physical chemistry is the part of chemistry that seeks to account for the properties and transformations of matter in terms of concepts, principles, and laws drawn from physics. This glossary is a compilation of definitions, descriptions, formulae, and illustrations of concepts that are encountered throughout the subject. This section describes the concepts that begin with the letter N; where appropriate, the entries also describe subsidiary but related concepts. Refer to the Directory for a full list of all the concepts treated.

The neighbouring-group contribution is the contribution to the chemical shift of a nucleus caused by a nearby group of atoms. It arises from the magnetic moment induced in the group by an applied magnetic field. The contribution to the shielding constant, σ, in a freely tumbling molecule is
where χ and χ are the magnetic susceptibilities of the group parallel and perpendicular to its symmetry axis, θ is the angle between the axis of the group and the vector from it to the nucleus of interest, and r is the distance of the nucleus.

The nematic phase of a liquid crystal mesophase is the phase in which molecules are aligned parallel to one another but lack other spatial organization (Figure N.1).

Figure N.1

The nematic phase of a liquid crystal.

Figure N.1

The nematic phase of a liquid crystal.

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The Nernst diffusion layer (Figure N.2) is a model of the concentration profile at the interface of an electrode and electrolyte solution in which the concentration falls linearly from a plane at a distance δ from the outer Helmholtz plane (OHP).

Figure N.2

The Nernst diffusion layer.

Figure N.2

The Nernst diffusion layer.

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The Nernst equation expresses the zero-current cell potential, Ecell, in terms of the standard cell potential, E cell , and the reaction quotient, Q, for the cell reaction:
where ν is the stochiometric coefficient of electrons in the matching half-reactions into which the cell reaction can be divided. At equilibrium, the cell potential is zero and Q = K, the equilibrium constant of the cell reaction. Therefore, an implication of the equation is that
If the cell reaction is of the form Reactants + νp H+(aq) → Products, then the cell potential depends on pH as

The Nernst heat theorem states that the entropy change accompanying any physical or chemical transformation approaches zero as T → 0. See Third law of thermodynamics.

Neutrons slowed to speeds close to those characteristic of room temperature have wavelengths close to 100 pm, and hence are suitable for diffraction by molecules. Neutrons pass through the electronic structure and are scattered by interactions with nuclei through the strong force. This scattering can be markedly different for isotopes and for elements that are neighbours in the periodic table. Moreover, a neutron has a magnetic moment, and the interaction of this moment with the electron spin magnetic moment, which is called magnetic scattering, modifies the scattering pattern. Thus, neutron diffraction is especially useful for studying magnetically ordered lattices. In inelastic neutron scattering, the scattering of a neutron results in the transfer of energy between it and the target molecules. An analysis of the spectrum of energy exchange gives information about the dynamical properties of liquid samples.

A fluid is in a state of Newtonian flow if it can be regarded as streaming in a series of layers or laminas (Figure N.3). The layer adjacent to the wall is stationary and successive layers have increasingly greater speeds.

Figure N.3

Newtonian flow.

Figure N.3

Newtonian flow.

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Newton’s law of cooling states that the rate at which a system cools is proportional to the difference in temperature, ΔT, between it and its surroundings:
where c is a constant that depends on the heat capacity of the sample and details of its thermal contact with its surroundings. Thus, the temperature of the system falls exponentially to the temperature of its surroundings (Figure N.4).
Figure N.4

Newtonian cooling.

Figure N.4

Newtonian cooling.

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A node is a point, line, or plane at which a wavefunction passes through zero (Figure N.5). Note that the wavefunction must pass through and not merely approach zero. A radial node is a node at a point in a radial wavefunction; an angular node is a plane dividing regions of opposite sign in an angular wavefunction. A nodal plane occurs in molecular orbital theory where there is complete destructive interference between atomic orbitals contributed by neighbouring atoms. It is typically associated with antibonding character in that region. The wavefunction of the ground state of a system has no nodes; it is generally the case that the energy of a system increases with the number of nodes in its wavefunctions.

Figure N.5

A nodal point and a nodal plane.

Figure N.5

A nodal point and a nodal plane.

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A nonbonding orbital is a molecular orbital that when occupied is neither bonding nor antibonding between two neighbouring atoms. It is commonly denoted n. Typically, a nonbonding orbital might be a lone pair on one atom or, in an ABC molecule, a molecular orbital that has contributions from A and C but not from B.

A normal mode is a collective, independent, synchronous motion of atoms or groups of atoms that leaves the centre of mass and the orientation of the molecule unchanged (Figure N.6). Provided the extension remains small and the potential is parabolic, a normal mode may be excited without leading to the excitation of another normal mode. Each normal mode has the energy levels of a harmonic oscillator:
where kf,Q is the force constant for the mode Q and μ is its effective mass, a measure of the mass that is moved in the course of the vibration. The force constant is in general a mixture of a variety of different terms: it is generally smaller for normal modes that are largely bending distortions of the molecule than for normal modes that are largely stretching distortions.
Figure N.6

Four normal modes of an AB4 molecule.

Figure N.6

Four normal modes of an AB4 molecule.

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The number of normal modes of a nonlinear molecule consisting of N atoms is 3N – 6; if the molecule is linear then the number of normal modes is 3N – 5. Normal modes cease to be dynamically independent of each other when anharmonicities are present. A normal mode is classified as infrared active if it corresponds to a changing electric dipole moment of the molecule. It is classified as a Raman active if it corresponds to a changing polarizability. The exclusion rule states that a normal mode of a molecule with centre of inversion cannot be both infrared and Raman active (it may be inactive in both).

A wavefunction ψ is said to be normalized (to 1) if
where the integration is over all space. When this condition is satisfied, the Born interpretation identifies ψ*ψ as a probability density, not merely as proportional to a probability density. A wavefunction that is not normalized can be normalized by forming and finding the normalization factor N such that

Nuclear magnetic resonance (NMR) is the resonant absorption of radiofrequency electromagnetic radiation by magnetic nuclei in a magnetic field (Figure N.7). In its simplest form, nuclei are exposed to a magnetic field and the frequency of an incident field is varied until a strong resonant absorption is observed.

Figure N.7

The energy levels of a proton in a magnetic field.

Figure N.7

The energy levels of a proton in a magnetic field.

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Nuclei of atoms of the same element come into resonance at different frequencies for two principal reasons. One is that they occupy different local magnetic environments, with the chemical shift, σ, defined through
where B 0 is the applied magnetic flux density. The resulting resonance frequencies are reported on the δ-scale, with

The resonance of a group of equivalent nuclei is split into a set of absorption frequencies known as fine structure by spin–spin coupling, their magnetic interaction with groups of nearby magnetic nuclei, with a splitting denoted J. If the latter group consists of N nuclei with spin quantum number I = 1/2, the resonance of the first group is spit into N + 1 lines with a binomial intensity distribution (that is, with relative intensities given by Pascal’s triangle).

Modern techniques of NMR are all based on the use of pulses of radiofrequency radiation and the interpretation of the observed signal by using Fourier transform techniques.

In the nuclear Overhauser effect (NOE) in nuclear magnetic resonance, a spin relaxation process is used to transfer the population difference typical of one type of nucleus to another nucleus, so enhancing the intensity of the signal produced by the latter. The NOE enhancement is usually reported in terms of the parameter η, where
Here I A is the intensity of the signals due to nucleus A before saturation, and IA is the intensity after the X spin transitions have been saturated. If the only source of relaxation is the dipole–dipole interaction, η lies between −1 (a negative enhancement) for slow tumbling molecules and +½ (a positive enhancement) for fast tumbling molecules. The enhancement is proportional to 1/R 6. Therefore, for there to be significant dipole–dipole relaxation between two spins they must be close. For a heteronuclear spin system the maximal enhancement is
where γA and γX are the magnetogyric ratios of A and X.

The term nuclear statistics refers to the selective occupation of molecular rotational states that stems from the requirement of the Pauli principle. The rotation of a molecule may result in the interchange of identical nuclei, so the wavefunction must change in accord with the principle: that is, be unchanged for bosons (I = 0, 1, 2,…) but change sign for fermions (I = 1/2, 3/2,…). For spin-0 bosons, as in CO2, only even-J states are allowed (Figure N.8).

Figure N.8

Nuclear statistics and the exchange of spin-0 bosons.

Figure N.8

Nuclear statistics and the exchange of spin-0 bosons.

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For pairs of identical spin-1/2 fermions, the electronic and rotational contributions to the total wavefunction might all change in phase. Which values of the rotational quantum number, J, are allowed then depends on how the other contributions change (Figure N.9).

Figure N.9

Nuclear statistics and the exchange of spin-1/2 fermions.

Figure N.9

Nuclear statistics and the exchange of spin-1/2 fermions.

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For a homonuclear diatomic molecule in the state Σ g + 1 with nuclear spin I in its vibrational ground state, the ratio of populations is given by

The consequences of nuclear statistics include the appearance of rotational absorption spectra and thermodynamic properties, such as heat capacity. As the conversion of nuclear spins from a parallel to an antiparallel relative orientation is typically slow, even-J and odd-J molecules may constitute separable species. Thus, ortho-hydrogen (o-H2, Itotal= 1, odd J) and para-hydrogen (p-H2, Itotal= 0, even J), with H specifically the fermion 1H, persist and interconvert only slowly. As odd-J rotational states are associated with Itotal= 1 (with z-components +1, 0, and −1) and even-J rotational states are associated with Itotal= 0 and its single state, in an equilibrium sample of dihydrogen, specifically diprotium, 1H2, at room temperature, there is about three times as much ortho-hydrogen as there is para-hydrogen.

Nucleation refers to the presence of centres on which droplets of vapour or microcrystals of solid may form to enable a phase transition to occur.

In the nuclear model of an atom, the nucleus is the small, positively charged, massive cluster of nucleons (protons and neutrons) at its centre. A nucleus is characterized by the atomic number, Z, the number of protons present (and therefore the electric charge Ze), and the nucleon number (or mass number), A, the total number of nucleons present. A nuclide is an atom (not just its nucleus) of an element E with a specific atomic number and nucleon number, and is denoted E Z A . Nuclides with the same value of Z but different values of A (such as C 6 12 and C 6 13 ) are isotopes of the element E. Nuclides with the same nucleon number (such as C 6 12 and B 5 12 ) are isobars, and those with the same number of neutrons (such as C 6 13 and N 7 14 ) are isotones.

Nuclei are also characterized by their spin, their intrinsic angular momentum, with nuclear spin quantum number I. Nuclei with half-integer values of I are fermions and those with integer values (including 0) are bosons.

Nuclei with I > 0 possess a magnetic dipole moment
where γN is the (empirically determined, positive or negative) magnetogyric ratio of the nucleus, gI is likewise its g-factor, and μN is the (positive) nuclear magneton, μN= /2mp. Nuclei with I > 1/2 may also possess an electric quadrupole moment (a measure of the asymmetry of distribution of electric charge over the particle).

Unstable nuclei undergo a variety of transformations, with the ejection of particles (such as α-rays or β-rays, which consist of H 2 4 e 2 + and e , respectively) or photons (as γ-radiation) giving rise to radioactivity. They may also capture electrons from the inner extranuclear shells of the atom. If the process results in a change in atomic number, it amounts to the transmutation of the original element.

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