CHEM 4701 Lecture Notes - Lecture 16: Scandium, Libyan Dinar, Phenylalanine

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mauvedinosaur421

25 Dec 2014

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Ligand field theory for coordination complexes of transition metals. You have 3 different types of ligands: sigma donors, pi donors, pi acceptors. -> have 3 different types of interactions btwn a ligand and metal: ligand-to-metal sigma direction. Electrons come from ligand to metalgoing to orbital that"s sigma in character. Metals aren"t that electronegative, so might want to give electrons back to the ligand. Interaction btwn filled pi valenceorbital on metal and empty pi orbital on ligand (lumo) that has correct symmetry. Removes excess electron density from the metal --> often called pi-backdonation ligand always donates electrons through sigma bondmay or may not have pi donation like a lewis base. Lumo = pi* --> empty and pi in character --> pi acceting (allows pi backdonation. -> co = pi acceptor sigma-donors: . h, . ch3, alkyls, amines (nh3, nme3) pi-donors: filled sigma bond + filled pi orbital.

Related Questions

I want to find the Kn value of Cu(II) and EDTA. I was given the formula kn= [ML4]/[ML3][L]. 12.3 ml of edta was used to tritrate 0.1194 grams of Copper in 50 ml of water. The indicator used was murexide.

At the core of general acid-base theories, there is the concept of âtransferâ of one entity to another. In the case of BrÃ¸nsted-Lowry acid base theory, the transferred entity is the proton, and their transfer processes are widely exploited in chemical methods. In addition to proton transfer, electron pairs can also be donated/shared between donors and acceptors. In this case, an atom/molecule, which can accept a pair of electrons, is referred to as a Lewis acid while the entity donating the pair of electrons is referred to as a Lewis base. The most prevalent Lewis acid-base systems involve metal complexes with vacant nd-orbitals, as well as electron deficient systems including B, Si, Ge, etc. The Lewis acid base theory is also known as the Hard-Soft acid base theory (HSABT) with âhardnessâ defined as small highly charged species that are weakly polarizable (Lewis acids). In contrast, âsoftnessâ is described by species that are larger and highly polarizable species with low charge (Lewis bases).
In the case of metal chemistry, Lewis acid-base theory provides a means to describe the ability of âligandsâ to coordinate to metal ions as well as the stability of metal-ligand complexes. Recall that coordination bonds are the donation/acceptance of lone pairs of electrons to empty metal orbitals to another atom; the definition of Lewis acid-base chemistry! The stability of Lewis acid-base complexes can be described through the stability constant which is analogous to the Ka that describes BrÃ¸nsted-Lowry acidities. Many metal ions can coordinate (bind) many Lewis base ligands in a step-wise fashion according to:
M + L = ML K1 = [ML]/[M][L] Eq. 1
ML + L = ML2 K2 = [ML2]/[ML][L] Eq. 2
ML2 + L = ML3 K3 = [ML3]/[ML2][L] Eq. 3
MLn-1 + L = MLn Kn = [ML4]/[ML3][L] Eq. 4
and for which the free energy for this dissociation reaction is given by:
ÎG0 = -RTLnKn Eq. 5.
where R is the gas constant and T is the temperature in Kelvin.
Figure 1: Left- EDTA. Right- Typical EDTA-transition metal complex.
The ethylene diamine tetraacetic acid ligand (EDTA, a Lewis base) provides a mechanism to probe the Lewis acid strength of various metal complexes (Figure 1). This multi-dentate ligand (multiple Lewis base sites on a single ligand) forms complexes with metals of the form:
Mn+ + Y4- = MYn-4 Eq. 6
K = [MYn-4]/[Mn+][Yn-4] Eq. 7
where Y4- is the EDTA ligand.
In this experiment, the Lewis acid strength for two different metals will be examined by measuring the stability constants for the metal-EDTA complex. Of specific interest is the how the Lewis acid strength of the metal ion correlates with:
1) atomic/ionic radii, 2) oxidation state, 3) electron configuration, and 4) polarizability.
You will determine the stability constants of both a Cu2+- and Zn2+-EDTA complexes as well as the corresponding free energy. Using these data, you will compare the relative Lewis acidities of both metals and describe differences in terms of the metal ion properties described above.
.
Chemicals
CuSO4
ZnSO4
EDTA
Murexide
Instruments
Buret
Experimental
You and your group will determine the concentration and ultimately the free energy of Cu(II) and Zn(II) using the hexadentate chelating ligand, EDTA.
You will be given a ~100 mM standardized solution of EDTA (check the label for exact concentration prior to beginning). You will need to weigh ~0.1 g per metal salt sample. Dissolve the metal salt into 50 mL of DI water. Add 2-3 drops of murexide to your metal. After properly preparing your buret with EDTA, titrate your metal with EDTA. Repeat for a total of 3 titrations per metal.
1. Approximately how much EDTA will you need for each titration assuming the metal-saltsâ masses are accurate?
2. What type of indicator is murexide and what color will its endpoint be?
Post-Lab Questions
1.
a) Using the equations given in the introduction and your titration results, what are the Kn of the EDTA-Copper complex? Show calculations.
b) Using the equations given in the introduction and your titration results, what are the Kn of the EDTA-Zinc complex? Show calculations.
2. What are the corresponding ÎG values for the EDTA-metal complexes? Show your calculations
3. Would copper be considered a hard or soft lewis acid? What about zinc? Describe what makes these metals hard or soft.
4. What trends would you predict for EDTA-metal complex Kn and ÎG values when:
a) going down a row of transition metals of the same oxidation state?
b) of the same transition metal with increasing oxidation state? (For example, Iron can exist as Fe(II), Fe(III), Fe(IV), and higher oxidation states)
5. Discussion (formal report style): Compare and contrast the concepts of Lewis and BrÃ¸nsted-Lowry acids and bases. Support these concepts with your data over the last two weeks and with research. Cite your sources.

The conduction of electricity inmaterials is explained in terms of band theory. The band that isformed from the filled bonding molecular orbitals is called thevalence band, and the band that is formed from the emptyantibonding molecular orbitals is called the conductionband. The energy difference between these bands is known as theband gap energy, or the band gap.

Click on the image below to explore the activity, which will help you to identify the insulator and thetypes of semiconductors based on band gap energy. Blue-coloredbands indicate conduction bands, and red-colored bands indicatevalence bands.

When you click on each box, you will observe the changes in bandgap energy for that material.

Part A

In the interactive activity, the bandshown at the top is the conduction band, and the band shown at thebottom is the valence band. The valence band consists of bondingmolecular orbitals that are filled with electrons, and theconduction band consists of vacant antibonding molecular orbitals.The red color indicates that the orbitals in that band are filledwith electrons, and the blue color indicates that the orbitals inthat band are empty. The space between the two bands shows theenergy difference between them and is known as the band gapenergy, or the band gap.

Which of the following statements are correct with respect tothe band structure and the band gap of different materials?

Check all that apply.

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Part B

When you add a controlled amount ofsubstance known as an impurity to a pure semiconductor, itsconductivity increases. This process is known as doping. Theaddition of an impurity can increase or decrease the number ofavailable electrons. If the number of electrons is increased, theextra electrons conduct electricity. If the number of electrons isdecreased, a vacant hole is created. The adjacent electron entersthe vacant hole and conducts electricity. Thus, it seems like theholes act as charge carriers. They are considered to be positivecharge carriers. Depending upon the charge carriers that conductelectricity, there are two types of semiconductors: p-typesemiconductors and n-type semiconductors.

Which of the following statements are correct with respect tosemiconductors?

Check all that apply.

	The undoped semiconductor has a partiallyfilled conduction band.
	The n-type semiconductor has apartially filled valence band.
	The p-type semiconductor has apartially empty conduction band.
	The p-type semiconductor has apartially empty valence band.
	The band gap of a semiconductor is lessthan that of an insulator.
	The conduction band for insulators isalways vacant.

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Part C

Germanium is a group 4A semiconductor. Theaddition of a dopant atom (group 3A element) that has fewer valenceelectrons than the host atom results in a p-typesemiconductor. The addition of a dopant atom (group 5A elements)that has more valence electrons than the host atom results in ann-type semiconductor.

Which of the following elements when used for doping germaniumwill yield p-type semiconductors, and which elements whenused for doping germanium will yield n-typesemiconductors?

Drag the appropriate elements totheir respective bins.

	The conductivity of semiconductors can beincreased by the doping process.
	The addition of group 3A elements to group4A semiconductors decreases the conductivity of the group 4Asemiconductors.
	As the temperature increases, theconductivity of semiconductors decreases.
	Holes are charge carriers in p-typesemiconductors.
	The addition of group 5A elements to group4A semiconductors increases the conductivity of the group 4Asemiconductors.
	Electrons are charge carriers inn-type semiconductors.