Experiment #4

Experiment #5

Molecular Dipole Moment

Ha, I am in a dipole moment! Dipole Moment

 Permanent dipole moment arises from an asymmetric distribution of electrical charge in the molecule, hence polar molecules   r  r d 

 A separation of one electronic charge (1.60  10-19 C) of 1.00 Å from an equal and opposite charge gives a dipole moment of 1.60  10-29 C·m or 4.80 Debyes (D, a CGS unit, not an SI unit) Peter Debye

 Peter Joseph William Debye (March 24, 1884 – November 2, 1966) was a Dutch physicist and physical chemist, and Nobel laureate in Chemistry.  From 1934 to 1939 Debye was director of the physics section of the prestigious Kaiser Wilhelm Institute in Berlin. From 1936 onwards he was also professor of Theoretical Physics at the Frederick William University of Berlin. These positions were held during the years that Adolf Hitler ruled Nazi Germany and, from 1938 onward, also over Austria.  In 1939 Debye traveled to the United States of America to deliver the Baker Lectures at Cornell University in Ithaca, New York.  After leaving Germany in early 1940, Debye became a professor at Cornell, chaired the chemistry department for 10 years, and became a member of Alpha Chi Sigma.  Debye remained at Cornell for the remainder of his career. He retired in 1952, but continued research until his death. Experimental Measurements

 The dipole moment of individual solute molecules

can be related to the dielectric constant (er) and refractive index (n) of the total solution  In a parallel plate capacitor, the external electric field causes the bound charges to be distorted such that a layer of induced negative charge will reside next to the positively charged plate and vice versa Net Charges

 Permanent dipole (): specific alignment  Induced dipole: polarizability (a) - - - - -  HARD: H2O, OH , CH3COO , F , NH3, oxalate ( OOC-COO ), en. - - -  SOFT: Br , I , SH , (CH3)2S, S=C(NH2)2 (thiourea), - P(CH3)3, PPh3, As(CH3)3, CN , -S-C≡N (thiocyanate S- bound)

 INTERMEDIATE: C6H5N (pyridine), N3- (azide), -N=C=S (thiocyanate, N-bound), Cl-

+ Polarizability

 Relationship between the polarization of the sample (P), the applied field (E), and the

sample dielectric constant (er) is

-12 2 -1 -2 -1 vacuum permittivity constant eo = 8.85  10 C N m J

PEee0  r 1 net dipole moment C per unit volume er  (depending on both C o polarizability and permanent dipole) Clausius-Mossotti Equation

 Local field (F) at the site of the molecule P P F  E  E  3e ee1 0 0  r 

31ee   PF 0 r 31ee e  2 0  r  N0  r  a e r  2 M  N 0   As P   a F  M  e 1 M N a r  0 e  2  3e Molecular r 0 polarizability Molar Polarization, PM Polar Molecules

2 , permanent dipole a  a o   3kT distortion polarizability

er 1 M N0 2 PM   ao   3kT er  2  3e0

2 N o N o  Pd  a o P  3eo 9eo kT Distortion Orientational 9eokT Polarization Polarization   P No Polarizability

 If high frequency AC is applied to the capacitance cell, then the permanent dipole of the molecules cannot rotate fast enough to follow the applied field and only the distortion term contributes to the molecular polarizability. Under these conditions the molar polarization only comes from distortion, Pd. 2  Measurement of the refractive index (n = er) of the substance at optical frequencies allows calculation of Pd.  In principle, measurement of PM at two temperatures allows ao and  to be determined. Polarizability

 The equations derived above apply best to substances in gas phase where intermolecular interactions are weak  Experimentally we may apply them to very dilute solutions Dilute Solutions

 The constants “a” and “c” can  3M acbe determined from 1 knowledge of how dielectric P  222 constant and refractive index 1 e  2 n  2 r1  1  depend on solution composition.

e  e  aX 2 r r1 9e kT 2 2 o n  n1  cX2   P No  X2 is the mol fraction of solute, er is the dielectric constant of the solution and n2 is the square of the refractive index of the solution  Linear regressions lead to the quantification of “a” and “c” Experimental Procedure

 Capacitance meter C e   r Capacitance  dielectric constant (er) C o  Refractometer  Refractive index (n)

2 solution # Chlorobenzene (g) cyclohexane (g) Mol fraction (X2) εr n n 1 0.5 64 2 1 64 3 2 64 4 3 64 solution o-dichloro- # benzene (g) cyclohexane (g) 5 0.5 64 6 1 64 7 2 64 8 3 64 Data Analysis

e  e  aX 2 2 r r1 2 n  n1  cX2

2 x e x n r x x x x x x 2 n1 er1

0 X2 0 X2 Data Analysis

 3M ac 1  P  222 1 e  2 n  2 r1  1 

9eokT http://macro.lsu.edu/howto/solvents/Dipole%20Moment.htm   P No

M1 = molar mass of cyclohexane in kg/mol 1 = density of cyclohexane in kg/m3 er1 = dielectric constant of cyclohexane (no units) n1 = refractive index of cyclohexane (no units)