CHEM 17

Exercises Coordination chemistry & Electrochemistry

[1]

Thermochromic complex. Solid [(CH3CH2)2NH]2[NiCl4] is a thermochromic complex. At low temperatures, it

is light yellow in color, but when heated to 72C, it changes to a brilliant blue color. X-ray diffraction (XRD)
experiments revealed the crystal structure of this complex at low and high temperatures. At low temperatures,
the [NiCl] unit occurs as an extended sheet, while at high temperatures, the [NiCl] unit occurs as isolated
tetrahedra in the lattice.

[1-1]

Identify the coordination numbers of Ni for the low T and high T forms of the complex.

[1-2]

Using thermodynamics, account for the structural changes that accompanied the change in
temperature. That is, explain why the extended [NiCl] sheets are stable at low temperatures, while the
isolated [NiCl] tetrahedra are preferred at higher temperatures.

[1-3]

Using crystal field theory, account for the difference in color observed in the low T and high T forms
of the complex.

The complex is also soluble in water. When dissolved in water, the resulting aqueous solution appeared green.
Heating or cooling this solution did not change its color.
[1-4]

[2]

Draw the structure of the complex responsible for the green color.

Determining Kf. The following cell:

Hg(l)| HgI42(0.001 M), I(0.500 M) || H+ (0.1 M) | H2 (0.1 bar) | Pt(s)
has a potential of 0.0534 V at 298 K. Given: E0red(H+/H2) = 0.00 V, E0red(Hg2+/Hg) = +0.85 V
[2-1]

Write the balanced equation for the cathode half reaction.

[2-2]

Write the balanced equation for the anode half-reaction.

[2-3]

Calculate the standard reduction potential for the anode half-reaction at 298 K.

[2-4]

Calculate Kf of HgI42.

[3]

[4]

Redox chemistry of plutonium. Given the Latimer diagram below of plutonium under acidic conditions.

[3-1]

Write the balanced equation for the reduction half-reaction PuO2+ Pu4+.

[3-2]

Calculate the standard reduction potential for PuO2+ Pu4+.

[3-3]

Identify which plutonium species will disproportionate spontaneously.

[3-4]

Identify which plutonium species will be the products of spontaneous comproportionation.

Redox chemistry of nitrogen. Given the Frost diagram below for nitrogen under acidic (plotted in solid line)
and basic (plotted in broken line) conditions.

[4-1]

Identify the most thermodynamically stable nitrogen species under acidic conditions.

[4-2]

Identify the most thermodynamically stable nitrogen species under basic conditions.

[4-3]

Identify one nitrogen species that will disproportionate spontaneously under basic conditions.

[4-4]

Give a comproportionation reaction that is spontaneous under acidic conditions.

[4-5]

Identify which species, and under what conditions (CHOOSE: acidic OR basic) is the strongest
oxidizing agent.

[4-6]

Identify which species, and under what conditions (CHOOSE: acidic OR basic) is the strongest
reducing agent.

Nitrogen fixation is the process in which atmospheric N 2 is converted to ammonia. This process is essential for
all life forms as it makes nitrogen a primary component of the biomolecules of life, accessible for nutrition.
There are nitrogen fixing bacteria found in soils that produce the ammonia naturally occurring in the soils.
These bacteria produce the naturally occurring fertilizers that aid in plant growth. Interestingly, these
nitrogen fixing bacteria work best under slightly acidic pH.
[4-7]

Account for the improved nitrogen fixation at slightly acidic pH, as compared to slightly alkaline
conditions.