Answers to CHEM1101 Quiz 2

1. The molecular orbital diagram is filled with the valence electrons of the molecule or molecular ion with a maximum of 2 electrons in each molecular orbital. Where there are two orbitals with the same energy, as for the and * orbitals on the diagram, the electrons occupy each orbital separately before pairing up. This minimises the repulsion between the electrons (Hund's rule). Paramagnetic molecules have unpaired electrons whereas diamagnetic molecules have all of the electrons paired. The bond order is calculated using: bond order = 1/2 (number of bonding electrons - number of antibonding electrons) The bonding orbitals are those labelled and and the antibonding levels are those labelled * and *. CN- has the highest bond order of molecules in the question and is diamagnetic. CN- has 10 valence electrons (4 from C, 5 from N and 1 from the negative charge). These occupy the orbitals as shown below.

As shown, the molecule has no unpaired electrons: it is diamagnetic. There are 8 electrons in bonding orbitals (4 in and 4 in ) and 2 electrons in antibonding orbitals (2 in *). Hence, the bond order is: bond order = 1/2 (8 - 2) = 3 The correct answer is C. 2. When electrons occupy a bonding orbital, they strengthen the bond. When electrons occupy an antibonding orbital, they weaken the bond. Anti-bonding bonding orbitals have a node (are zero) between the atoms which is part of a plane that is perpendicular to the bond. Bonding orbitals do not have such a node. Orbital II is a bonding orbital. It is a bonding orbital. There is not a node between the atoms:

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The correct answer is B. 3. The and part of the orbital label refers to the symmetry of the orbital around the bond. orbitals (whether they are bonding or * antibonding) are symmetric around the bond. They do not have a node lying along the bond. orbitals (whether they are bonding or * antibonding) are zero (have a node) along the bond. The correct answer is B. 4. Hydrogen bonds ("H-bonds") are especially strong intermolecular forces between a highly - atom and a highly + hydrogen atom. They require: a lone pair on an electronegative atom a hydrogen atom that is itself bonded to an electronegative atom Only N, O and F are sufficiently electronegative to form short and strong H-bonds.

Only NH3 fits the requirements listed above and form hydrogen bonds. The correct answer is B. 5. Ionic solids and covalent networks have strong bonds between all of the atoms in the solid. They tend to have very high melting points as melting them requires breaking of chemical bonds (and not intermolecular bonds). Hydrogen bonds tend to be the strongest intermolecular forces, except in large molecules. If hydrogen bonds have to be broken to melt a substance, the melting point tends to be quite high. Dispersion forces are strong for large molecules and for molecules containing atoms with many electrons. Molecules which possess dipole moments interact via dipole-dipole interactions. He possesses only 2 electrons and has no dipole moment so only very weak dispersion forces must be overcome to melt it. CH4 posseses more electrons and so has stronger dispersion forces than He. CH3 OH is able to form strong hydrogen bonds as it possesses hydrogen bonds to an electronegative element. H2 O is able to form 2 strong hydrogen bonds per molecule, as each molecule contains 2 H atoms and 2 O lone pairs,

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so forms more hydrogen bonds than CH3 OH. SiO 2 is a covalent network and the strong chemical bonds between the atoms must be broken to melt it. The order of increasing melting points is therefore: He < CH 4 < CH3 OH < H 2 O < SiO2 The correct answer is D. 6.

Functional group (B) is a ketone as the carbonyl carbon is bonded to two C atoms. In an aldehyde, the carbonyl carbon is bonded to at least one H atom. The correct answer is B. 7. The shape of a molecule can be determined using Valence Shell Electron Pair Repulsion (VSEPR) theory: 1. Draw the Lewis structure of the molecule 2. Count the number of bonding pairs and lone pairs around the atom of interest (a bonding pair can be a single, double or triple bond). 3. Use the table below to determine arrangement that minimizes the repulsion between these pairs. 4. The molecular shape or molecular geometry is the arrangement of the bonds around the central atom. Whilst the lone pairs determine what that is, they are not included in describing the molecular geometry.

number of sets of electron pairs

2 3 4 5 6 7

geometry of sets of electron pairs

linear trigonal planar tetrahedral trigonal bipyramid octahedron pentagonal bipyramid

Nitrogen has 5 valence electrons and each of the two O atoms has 6 valence electron. As there is a negative charge, there are thus: total number of valence electrons = 5 (N) + 2 6 (O) + 1 (negative charge) = 18 The Lewis structure is shown below:

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There are 3 sets of electron pairs around the central N atom: 1 single bond, 1 double bond and 1 lone pair. From the table above, these will arrange themselves in a trigonal planar arrangement. The molecular geometry is the arrangement of the bonds:

The molecular geometry is described as being bent. The correct answer is B. 8. Iodine has 7 valence electrons and each of the two Cl atoms has 7 valence electrons. As there is a negative charge, there are thus: total number of valence electrons = 7 (I) + 2 7 (Cl) + 1 (negative charge) = 22 The Lewis structure is shown below:

There are 5 sets of electron pairs around the central I atom: 2 bonds and 3 lone pairs. From the table above, these will arrange themselves in a trigonal bipyramid. The lowest overall repulsion between the electron pairs is achieved by placing all three lone pairs in the trigonal plane. Although this leads to an angle of 120o between the lone pairs, it means that each lone pair is 90o away from only two bonds. Other arrangements lead to 90o angles between lone pairs. The repulsions at 90o are much greater than those at 120 o so the former arrangement has lower energy and is the one adopted. The molecular geometry is the arrangement of the bonds:

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The molecular geometry is described is linear. The correct answer is B. 9. In X-ray fluorescence, electrons are accelerated from a cathode through a potential into a metal target anode. When the electrons strike the anode they collide the metal atoms and emit X-rays. These X-rays are called Bremsstrahlung radiation. When an electron collides with the atoms on metal surface, it may take more than one collision to stop the electron leading to a broad spectrum of X-rays being generated as shown by the figure on the quiz paper. The maximum energy of the X-rays corresponds to the electrons being stopped by a single collision. Electrons accelerated by a potential of 45 kV (45000 V) have an energy of 45 keV (45000 eV). As 1 eV is equal to 1.602 10 -19 J, the energy of the electrons is: E = (45000 eV) (1.602 10-19 J/eV) = 7.209 10-15 J This is the maximum X-ray energy. For X-rays (and any electromagnetic radiation), the energy and wavelength, , are related by: E = hc / or = hc / E where h is Planck's constant and c is the speed of light. Hence, the wavelength of the maximum energy X-rays produced is given by: = hc / E = (6.626 10-34 J s) (2.998 108 m s-1) / (7.209 10 -15 J) = 2.8 10-11 m or 0.028 nm 10. Atomic Absorbance Spectrophotometry (AAS) is used to measure the concentration of a particular atom in a sample that may contain a complex mixture. The Beer-Lambert Law relates the absorbance, A, of a sample to the cocentration, c, of the atom that is absorbing light: A = cl where l is the optical path length and is the extinction coefficient, which is a property of the element being examined. If the absorbance of a known concentration of an atom is known, the absorbance of an unknown concentration can used to work out this unknown concentration. For the reference sample of gold, c = 0.20 ppm and A = 0.33 so the Beer-Lambert Law gives: A =cl 0.33 = (0.20 ppm) l or l = (0.33 / 0.20 ppm) = 1.65 ppm -1

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When the absorbance A = 0.0054, the cocentration of gold is therefore: c = A / l = (0.0054) / (1.65 ppm-1) = 0.0033 ppm

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