CHY 103 Lecture Notes - Lecture 3: Redox, Oxidation State, Covalent Bond

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18 Jul 2016

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Other reaction types (note: this material is not in your text) In observing various types of reactions and learning to write net ionic equations we have seen that atoms and molecules may possess various degrees of charge, e. g. iron can be fe (s), fe2+, fe3+ . The ________________________________ is a formal way to keep track of electrons in redox reactions. It assumes that the more electronegative atom in a covalent bond will >take= all the electrons rather than share them. Oxidation: loss of electrons by an atom, molecule, ion, etc. e. g. reduction: gain of electrons by an atom, molecule, ion, etc. Oxidation: loss of electrons by an atom, molecule, ion, etc. e. g. reduction: gain of electrons by an atom, molecule, ion, etc. e. g. 1. Examples: assign oxidation numbers to all the atoms in the following: A redox reaction involves both a gain and loss of electrons, i. e. both an oxidation and a reduction occurs.

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.

Practice problems for exam 2 ______________

Useful Information:

h=6.626Ã10-34JÂ·s.; c=3.0Ã108 m/sec; E=hï® ; E= hc , ï¬ = h/mv; 1J = 1 kg-m2/s2 ï¬

mass of electron = 9.11 Ã 10-28 g, ïE= q + w ; 1 cal = 4.184 Joules Please Show all Work

1. Which of the following substances have standard heats of formation that are equal to zero by definition (circle your answers): H2(g), H(g), O3(g), H2O(s), H2O(l), Hg(l), Hg(s), Hg(g).

2. Limestone stalactites are formed in the reaction: Ca2+(aq) + HCO3-(aq) ï CaCO3(s) + CO2(g) +

H2O(l)
If one mole of CaCO3 is produced at 298 K under one atmosphere of pressure, the reaction performs 590 calories of expansion work, pushing back the atmosphere as CO2 is formed. At the same time, 9310 calories of heat are absorbed from the environment. What is ïE in Kcal/mole for CaCO3.

3. What is the minimum wavelength of light in AÌ (1 AÌ = 10-8 cm) needed to provide enough energy per quantum to rupture the chemical bond in hydrogen iodide (HI). The bond dissociation energy of HI is 71.4 Kcal/mole.

4. Sketch the shape and orientation of the following types of orbitals: s, px, dxy, dz2, dx2-y2

5. Give the values of (n) , (l) and (ml) for each orbital in the 4p subshell.

6. Write the complete electron configuration for the following: Ti 2+_____________________________________ Cr_______________________________________

N______________________________________

7. Calculate the standard enthalpy of formation ( ï Ho) for diamond from graphite [i.e. C (graphite) ï C (diamond)] given that:

C (graphite) + O2 ï CO2 (g) ( ï Ho = -393.5 KJ/mole) C (diamond)] + O2 ï CO2 (g) ( ï Ho = -395.4 KJ/mole)

If 1.0g of graphite is converted to diamond, what is the energy change? Is this an endothermic or exothermic reaction?

8. An 160 pound astronaut on his way to Mars is buzzing along at 10,000 miles per hour. (a) Express his weight in grams (one pound = 454 grams) so that you can calculate the astronautâs wavelength (1mile/hour = 44.7 cm/sec)

(b) Suppose the astronaut detects outside his spacecraft a proton (m=1.7 x 10-24 g) from a âsolar windâ moving at exactly the spacecraft velocity. What is the proton wavelength is in AÌ (1 AÌ = 10-8 cm.

9. What is the maximum number of electrons that can occupy each of the following subshells? a) 3d_________________ b) 1s____________________ c) 2p ____________________

10. Identify the element represented by the following electronic configuration.

a) [Ne] 3s2____________________

b) What is the electron configuration for the first excited state of this atom.______________

11. Determine the number of valence electrons for each element.
(a) Br___________ (b) Na _________ (c) Sn __________

12. 175 g of Fe at 15.0oC is mixed with 225 g of H2O at 95.0oC. What is the final temperature of the mixture? The specific heats of iron= 0.448 J/g oC and water = 4.184 J/g oC). (keep in mind the following: heat gained + heat lost = 0 and q=mass x heat capacity x ïT)

13. (5 pts) Calculate values of ÎHrxn for the following reactions: CS2(g) + 3O2(g) ï® CO2(g) + 2SO2(g)

The heat of formation for the following substances is given in kJ/mol:

CS2 CO2 SO2 117.4 -393.51 -296.83

14. (6 pts) Use the electron configuration of Li and Be and determine which element has the greatest second ionization energy. Defend your answer.

15. Mark beside each of the following processes either âexoâ or âendoâ according to whether you think the process will release heat or absorb heat.

a. Ca(g) ï Ca(g)+2 + 2e-
b. I(g)+1e-ï I(g)-1
c. Ca(g)+2 + S(g)-2 ï CaS(s) d. I2(g)ï 2I(g)

( ) ( ) ( ) ( )

16. (6 pts) In each of the following pairs, which of the two species is larger?
a) O-2 or Na+ b) Ti+4 or Ti+2 c) B or C d) N or N-3

17. Write down the Lewis dot structure for the following (a) N_______________ (b) Ne________________

18. THE BORN HABER CYCLE: I may have a problem on the Born Haber cycle. Please check my lecture notes to see how to set up the process and then calculate the lattice energy from the various thermodynamic quantities such as in the NaCl example below;

ï H ï¯ f NaCl = -411KJ

Na(s) ï® Na(g) ï H =108KJ
1â2 Cl2 ï® Cl(g) ï H = 122KJ Ionization Energy of Na ï H = 496 KJ Electron affinity of Cl ï H = -349KJ

CHY 103 Lecture Notes - Lecture 3: Redox, Oxidation State, Covalent Bond

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