Introduction to Molecular and Nanoscale Principles (NME 220) Homework 7 Solution

due: May 18, 2012

Reading Assignment in Course Textbook: Course Textbook: Chapter 4 (Section 4.1-4.2.3); Chapter 10 (Section 10.2.1) Lectures: Lecture notes on Interactions in particular: Dipolar Interaction

A. Narrative Overview Questions

1.1. Provide approximate magnitudes of the interaction energies of ionic, covalent, hydrogen and Van der Waals (VdW) bonds. Answer: Approximate interaction energies are as follows: - Ionic: ~150-250 kcal/mol - Covalent: ~150-300 kcal/mol - Hydrogen: ~2-40 kcal/mol NH:O ~2 kcal/mol, NH:N ~3 kcal/mol, OH:N ~7 kcal/mol, OH:O 5 kcal/mol, FH:F ~39 kcal/mol - VdW: ~1-5 kcal/mol CH4 ~2 kcal/mol N-butane ~5 kcal/mol 1.2. Briefly explain what is involved in hydrogen bonding. Which electronegative atoms are involved in hydrogen bonds? What are their electronegativities based on the Pauling scale. Answer: Hydrogen bonding leads to a strong attractive interaction between - a very electronegative atom (from another molecule or chemical group) - a tiny partially positive proton in form a hydrogen atom (covalently bonded to another electronegative atom) The following electronegative atoms are involved in hydrogen bonding: Electronegativity Values 3.04 3.44 3.98

- Nitrogen - Oxygen - Fluorine

Introduction to Molecular and Nanoscale Principles (NME 220) Homework 7 Solution

due: May 18, 2012

1.3. List at least three molecular groups, in which their compounds can interact via hydrogen bonds. Answer: Acid Amide Carboxylic Acid Alcohol Amine 1.4. What kind of interaction holds the -sheet in proteins together? Answer: Hydrogen bonds. The sheet is a regular secondary structure in proteins that connects beta strands laterally by five or more hydrogen bonds, forming a generally twisted, pleated sheet.

1.5. What is the relative permittivity of a medium? Answer: The relative permittivity of a medium is a measure of how an external electric field is modified, and in turn affects the medium. 1.6. List the three groups of VdW interactions. Answer: - Dynamic dipole-dipole forces (Keesom forces) - Induced dipole-dipole forces (Debye) - Dispersion forces (London) 1.7. What do they have in common concerning their interaction length dependence? Answer: all terms are proportional to 1/r6. 1.8. Sketch the interaction length dependence V(r) between attractive ionic interactions and attractive VdW interactions. Answer: Key is that ionic is proportional to 1/r while VdW are proportional to 1/r6. Attractive interactions are those for which the potential V(r) is negative. Repulsive interactions are those for which the potential V(r) is positive.

Introduction to Molecular and Nanoscale Principles (NME 220) Homework 7 Solution

due: May 18, 2012

1.9. Can VdW interactions be repulsive? Answer: Yes. VdW interactions can be repulsive depending on the sign and strength of the mediums permittivity. In air, Van der Waals forces are typically attractive, which explains the universal shape of the Lennard-Jones (LJ) potential. 1.10. What is the definition for the dipole moment? Answer: The dipole moment can be defined as a charge, q, displaced over a distance, l: u = ql 1.11. What is a Debye?
Answer: A Debye (D) is the CGS unit of the electric dipole moment. 1D = 3.3310-30 C m.

Introduction to Molecular and Nanoscale Principles (NME 220) Homework 7 Solution

due: May 18, 2012

1.12. How does the dipole moment compare between HCl, H2O and CO2? Explain the deviating dipole moment of CO2 in comparison to the two other molecules
Answer: from Yaws Chemical Properties Handbook:

Chemical CO2 H2O HCl

Dipole Moment (D) 0.00 1.85 1.08

CO2 has a zero dipole moment (non-polar molecule) due to its perfect symmetry.

1.13. Provide formally more insight into the Van der Waals interaction parameter C considering the variety of dipolar interactions. The expressions have to indicate the dependence on dipole moments, dielectric permittivity, polarizability, thermal dependence and quantum fluctuations.
Answer:

C = C Keesom + C Debye + C London

u4 3(4 o ) k BT 2u 2 o
2

/ Dispersion

In the following, identical molecules are assumed.

C Keesom =

C Debye =

(4 o )2
2 3 o h 4 (4 o )2

C London / Dispersion =

Introduction to Molecular and Nanoscale Principles (NME 220) Homework 7 Solution

due: May 18, 2012

B. Worked Problems
2.1. For a monovalent ion such as Na , the electric field at a distance of 0.4 nm from its center is E=e/(4or2) = 9 109 V/m. Estimate the distance by which the electron cloud of a methane (CH4) molecule is shifted relative to the center of the molecule due to the imposed electric field of the ion.
Methane polarizability from the Electronic Polarizability Table: o = 2.6 in units of 4o3.
+

Solution

u ind = 0 E = 4 oE 8.85 10 12 C 2 2.6 10 30 m 3 9 10 9 V J = 2.6 10 30 C m u ind = 4 1 J m m V C 30 u 2.6 10 C m = 0.016nm l = ind = e 1.62.6 10 19 C

This is about 8% of the molecular radius of methane (0.2 nm).

2.2. Determine the orientational polarizability of water at 300 K, and compare it to the value of the electronic polarizability. The dipole moment of water is 1.85 D, and its electronic polarizability is (1.48) (4o ) 10 30 m 3 or (1.48) 1.11 10 40 C 2 m 2 J 1 . Note the units: 4 o = 1.11 10 10 C 2 m 1 J 1
Solution uwater = 1.85 D(ebye) = (1.85 D) (3.336 10-30 C m D-1) = 6.17 10-30 Cm. The orientational polarizability is

orient =

u2 6.17 10 30 Cm = = 3.07 10 39 C 2 m 2 J 1 23 1 3k B T 3 1.38 10 J K (300K )

Introduction to Molecular and Nanoscale Principles (NME 220) Homework 7 Solution

or 2.76 (4o ) 10 29 m 3 orient 2.76 (4 o ) 10 29 m 3 = = 18.64 o 1.48 (4 o ) 10 30 m 3 and exceeds the electronic polarizability by a factor of ~ 20 at room temperature

due: May 18, 2012