Molecular Interactions, Chapter 17 General Objectives Description of molecular interactions in gases and liquids; Electric properties of molecules (electric

dipole moment and polarizability); Other properties (refractive index and optical activity); Properties of substances that originate from molecular interactions; Behavior of molecules in external electric fields; Cohesion of molecules and formation of bulk phases of matter. Electric Properties of Molecules Electric properties of molecules originate in competing influence of nuclei (with different charges) electric dipole moment Electric Dipole Moment Electric dipole: two electric charges (+Q, Q) separated by a distance R Dipole moment (vector from Q to +Q):
=QR

Common unit of the dipole moment: debye, 1D = 3.335 1030 C m

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Examples H2O: = 1.85 D HCl: = 1.08 D HI: = 0.42 D

Polar molecule: (i) a molecule with a permanent dipole moment; (ii) permanent dipole moment stems from the partial charges on the atoms; (iii) partial charges arise from differences in electronegativities Non-polar molecule: (i) it acquires an induced dipole moment in an electric field; (ii) distortion of electronic distributions is temporary and disappears upon the field removal Experimental method: Microwave spectroscopy is used to measure the electric dipole moments of molecules for which a rotational spectrum can be observed Dipole moment of heteronuclear diatomic molecules: / D electronegativity difference) More electronegative atom is normally the negative end of the dipole Molecular symmetry determines whether a polyatomic molecule is polar or not (

CHEM 221, Lecture 5-1 Molecular Interactions

Ozone (O3): (i) it is a homonuclear molecule; (ii) it is polar because the central O atom is different from the outer two it is bonded to two O atoms; (iii) the dipole moments associated with each bond make an angle to each other and do not cancel out Carbon dioxide (CO2): (i) it is a heteronuclear molecule; (ii) there are partial charges on all three atoms; (iii) the molecule is linear; (iv) the dipole moments associated with each CO bond are antiparallel and cancel out Dipole moment of polyatomic molecules: sum of individual contributions (vectors)

Two dipole moments (1, 2) that make an angle

2 res = 1 + 2 2 + 21 2 cos

res resultant dipole moment When 1 = 2 then res 2 1 cos /2

CHEM 221, Lecture 5-1 Molecular Interactions

Polarizabilities An applied electric field can distort a molecule and align its permanent electric dipole moment Induced dipole moment (*): polarizability of the molecule E field strength Observation: (i) The greater the polarizability, the greater is the induced dipole moment for a given E; (ii) in formal treatment vectors should be used the induced dipole moment might not be parallel to the applied field Unit of polarizability: C2 m2 J1 Polarizability is often expressed as a polarizability volume Polarizability volume (): ' = 4 o Unit of : m3 * = E

CHEM 221, Lecture 5-1 Molecular Interactions

Observation: Polarizability volumes are similar in magnitude to the actual molecular volume (~1030 m3 = 1 3) Polarizability volumes correlate with the HOMO-LUMO separations in atoms and molecules LUMO lies close to HOMO: polarizability is large LUMO lies high above HOMO: polarizability is low Molecules with small HOMO-LUMO gaps are typically large with numerous electrons Polarizability is anisotropic its value depends on the orientation fo the molecule relative to the field Example: (i) Polarizability volume of benzene with the field perpendicular to the ring: 0.0067 nm3; (ii) polarizability volume of benzene with the field in plane with the ring: 0.0123 nm3

CHEM 221, Lecture 5-1 Molecular Interactions

Polarization Polarization (P) of a sample is its mean electric dipole moment density
P=

mean electric dipole moment number density (number of molecules per unit volume) Dielectric sample: it is polarizable, non-conducting medium Polarization of an isotropic fluid sample is zero in the absence of an applied field (molecules adopt random orientation) = 0 Polarization of an isotropic fluid sample is non-zero in the presence of an applied field (dipole fluctuate but becomes partially aligned) z 0 z 2 E = 3k T

where z the direction of the applied field E

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At very high (strong) electric fields the orientations of the molecular dipoles fluctuate less about the field direction the mean dipole moment approaches its maximum value z =

Analysis: We analyze the behavior of molecular dipoles in an electric field that changes its direction Case 1: The applied field changes direction slowly the permanent dipole moment has time to reorient the whole molecule rotates into a new direction and follows the field Case 2: (i) The applied electric field changes direction fast (the frequency of the field is high) a molecule cannot change direction fast enough to follow the change in direction of the applied field then the permanent dipole moment makes no contribution to the polarization of the sample; (ii) because a molecule takes about 1 ps to turn through about 1 radian in a fluid, the loss of this contribution to the polarization occurs when measurements are made at f 1011 Hz (microwave region); (iii) the orientation polarization (polarization arising from the permanent dipole moments) is lost at such high frequencies

CHEM 221, Lecture 5-1 Molecular Interactions

Case 3: (i) The distortion polarization (polarization arising from the distortion of the positions of the nuclei by the applied field) is lost as the frequency is raised even more; (ii) at high frequencies the molecule is bent and stretched by the applied field, and the molecular dipole moment changes accordingly and the time taken for a molecule to bend is approximately the inverse of the molecular vibrational frequency; (iii) the distortion polarization disappears when the frequency of the radiation is increased through the infrared region Case 4: At even higher frequencies (visible region), only the electrons are mobile enough to respond to the rapidly changing direction of the applied field; (ii) the polarization that remains is now due entirely to the distortion of the electron distribution, and the surviving contribution to the molecular polarizability is called the electronic polarizability Observation: The disappearance of polarization occurs in stages; each successive stage occurs as the incident frequency rises above the frequency of a particular mode of vibration

CHEM 221, Lecture 5-1 Molecular Interactions

Relative Permittivities Potential energy of interaction of two charges (Q1 and Q2) separated by r in a vacuum V= q1 q 2 4 o r

o vacuum permittivity (dielectric constant of vacuum) Potential energy of interaction of the charges (Q1 and Q2) separated by r in a medium V= q1 q 2 4 r

permittivity of the medium (dielectric constant of medium) r relative permittivity (relative dielectric constant) r = o Observation: r affects the strength of interactions between ions (r(H2O) = 78 at T = 298 K Coulomb interaction energy of ions in water is 78 times lower than its value in the vacuum)
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Observation: r for a substance is large if its molecules are polar or highly polarizable Debye equation: mass density of sample M molecular weight Pm molar polarization Debye equation is a quantitative relation between the relative permittivity and the electric properties of the molecules
N Pm = A 3 o 2 + 3k T

r 1 Pm = r + 2 M

2 / 3kT stems from the thermal averaging of the electric dipole moment in the presence of the external electric field (see p. 6) Clausius-Mossotti equation: r 1 NA = r + 2 3M o

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Important: The Claucius-Mosotti equation is applicable when there is no contribution from the permanent electric dipole moment (molecules are nonpolar or the frequency of the applied field is so high that the molecules cannot orientate quickly enough to follow the change in direction of the field) Maxwell equations: they relate the refractive index at a (vis and UV) specified wavelength to the relative permittivity at that frequency: nr = r nr the refractive index; it is the ratio of the speed of light in a vacuum (c) to its speed (c) in the medium: nr = c/c Consequence: The molar polarization (Pm) and the molecular polarizability () can be measured at frequencies typical of visible light (f = 1015 1016 Hz) by measuring the refractive index of the sample and using the ClausiusMossotti equation Observation: Measurements of r at a series of temperatures allow one to calculate Pm; plot of Pm values vs. 1/T leads to the determination of and (slope = NA 2 / 9o k and intercept (at 1/T = 0) = is NA / 3o)

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Blackboard Example (Atkins, de Paula): The relative permittivity of camphor was measured at a series of temperatures with the results given below. Determine the dipole moment and the polarizability volume of the molecule. T / C / g cm3 r 0 0.99 12.5 20 0.99 11.4 40 0.99 10.8 60 0.99 10.0 80 0.99 9.50 100 0.99 8.90 120 0.97 8.10 140 0.96 7.60 160 0.95 7.11 200 0.91 6.21 M = 152.23 g mol1

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