INORGANIC CHEMISTRY II ICH 231T

SEMESTER TEST 3

DEPARTMENT OF CHEMISTRY 2013-04-22

Surname__________________________________________ Initials___________________________________________ Student number____________________________________ Course registered for________________________________ TIME ALLOWED: Strictly 1 hour FULL MARKS: 60 TOTAL MARKS: 63

THIS IS A FILL-IN PAPER. Write your answers clearly next to each question. QUESTION 1 1.1 Give chemical reactions to support the following statements regarding the chemistry of boron: 1.1.1 The chloride of boron reacts vigorously with water to form orthoboric acid. Give an intermediate step which shows water reacting as a Lewis acid. (2) Cl-B-Cl + H-O-H HCl + H-O-B-Cl Cl Cl 1.1.2 Successive action of water forms the final product. Give the overall reaction equation. (2) H-O-B-Cl +2H2O 2HCl + H-O-B-O-H Cl O-H 1.1.3 The Fluoride reacts differently and two acids are formed. 4BF3(g) + 3H2O(l) 3HBF4(aq) + H3BO3(aq) 1.2 What physical property and mode of action makes BF3 a useful Friedel-Crafts catalyst? (3) Small size & reactivity. Ability to act as electron pair acceptor (completes octet around boron). It is a strong Lewis acid.
1

(3)

1.3.1 Provide a balanced chemical reaction for the formation of borazine from ammonia and diborane 6NH3 + 2B2H6 = 2B3N3 H6+ 12H2 (3)

1.3.2 Borazine is isoelectric with benzene and shares many similar physical and chemical properties. Why does borazine react with HCl while benzene does not? (3) Boron is electropositive and highly susceptible to electrophile attack while nitrogen is electronegative and readily accepts protons. Benzene only has 6-carbon atoms which will attract neither electrophiles nor nucleophiles. 1.4 Give structural representations of the following molecules. Indicate which structure represents a 2-electron 3-center bond and which makes use of dative bonds. Indicate any dative bonds. 1.4.1 Trimethyl aluminium, Al2(CH3)6. (4)

Bridge formed by 2-electrons Al-C-Al 3-centered (iso-structural with diborane forms a similar bridging structure)

1.4.2 Aluminium chloride, Al2Cl6. Indicate dative bonds (4)[24]

Cl Al Cl

Cl

Cl Al

Cl

Cl

(unlike boron trichloride, an electron deficient planar monomer, aluminium chloride forms a dimer.)

QUESTION 2 2.1 The impure forms of graphite are classified as microcrystalline and have large surface areas. Give four types of impure graphite and state one major use of each. Coke reduction of metals from their oxides Carbon black printers ink, shoe polish Charcoal burning for heat fuel fires Activated carbon eg Animal charcoal charred bones an excellent absorbent 2.2 Carbon dioxide has a low solubility in water. Most of it is present as molecular CO2. During the interaction with water molecules carbonic acid is formed. Showing the movement of electrons suggest a mechanism for this reaction. (4) (8)

2.3

What factors contribute to the differences in reactivity of carbon and silicon? (3) Size silicon atom is larger, electronegativity silicon has lower electronegativity, carbon has no d-orbitals CO2 is a gas containing two -bonds while SiO2 is a solid network containing only bonds. Provide reasons for these differences in structure. (4)[19] Within a group smaller atoms are more likely to form -bonds because the atoms can move closer to allow strong overlap. Carbon is small enough to allow this while silicon is not(in order to form an octet it must polymerise)

2.4

QUESTION 3 3.1.1 In the formation of PCl5 phosphorous is said to expand the octet. Explain how this happens. (3) One of the pair of electrons in the 3s orbital moves to an available 3-d orbital creating 5 singly occupied orbitals where chlorine can attach.

3.1.2 Offer two reasons to support why this rearrangement never occurs with nitrogen. No d-orbital available for any electron rearrangement (Steric hindrance nitrogen is too small to accommodate five attachments) 3.2.1 What are the sources of the raw materials needed for the Haber process? Nitrogen is obtained from the air and hydrogen from synthesis gas (methane).

(2)

(1)

3.2.2 Nitrogen is produced industrially by the Haber process. Give a brief description of this process including the conditions, such as temperature and pressure at which this reaction occurs. (3) The reaction takes place at a high pressure of 250 atmospheres in the presence of a finely divided iron catalyst at 500 C 3.2.3 Provide a balanced chemical reaction for this process N (g) + 3H (g) 2NH (g)
2 2 3

(2)

3.2.4 State what influence an increase of pressure will have on this process and provide a valid reason for your statement. (3) More of the product (ammonia) will form fewer molecules in product = fewer collisions and counters the pressure increase. (Le Chateliers principle) 3.4 The most common allotropes of phosphorous are red and white. How do these two allotropes differ in terms of: 3.4.1 Structure (3) Both are P4, but white phosphorous exists as single tetrahedral units while in red phosphorous each of these single (P4) units have opened and they are joined together to form a more stable macromolecule 3.4.2 Reactivity (3)[20] White phosphorous is highly reactive and unstable due to strain on the ring and readily converts to the more stable red allotrope