Explain why alkyl groups act as electron donors when attached to a π system.
When an alkyl group is attached to a π system, it acts as an electron-donor group by the process of hyperconjugation. To understand this concept better, let us take the example of propene.
In hyperconjugation, the sigma electrons of the C-H bond of an alkyl group are delocalised. This group is directly attached to an atom of an unsaturated system. The delocalisation occurs because of a partial overlap of a sp3-ssigma bond orbital with an empty p orbital of the π bond of an adjacent carbon atom.
The process of hyperconjugation in propene is shown as follows:
This type of overlap leads to a delocalisation (also known as no-bond resonance) of the π electrons, making the molecule more stable.
What are hybridisation states of each carbon atom in the following compounds ?
(i) CH2=C=O,
(ii) CH3CH=CH2,
(iii) (CH3)2CO,
(iv) CH2=CHCN,
(v) C6H6
Explain the terms Inductive and Electromeric effects. Which electron displacement effect explains the following correct orders of acidity of the carboxylic acids?
(a) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
(b) CH3CH2COOH > (CH3)2CHCOOH > (CH3)3C.COOH
Write bond line formulas for : Isopropyl alcohol, 2,3-Dimethyl butanal, Heptan-4- one.
Give condensed and bond line structural formulas and identify the functional group(s) present, if any, for :
(a) 2,2,4-Trimethylpentane
(b) 2-Hydroxy-1,2,3-propanetricarboxylic acid
(c) Hexanedial
Indicate the σ and π bonds in the following molecules :
(i) C6H6,
(ii) C6H12,
(iii) CH2Cl2,
(iv) CH2=C=CH2,
(v) CH3NO2,
(vi) HCONHCH3
Identify the reagents shown in bold in the following equations as nucleophiles or electrophiles:
(a) CH3COOH + HO- → CH3COO- + H2O
(b) CH3COCH3 + C-N → (CH3)2 C (CN) (OH)
(c) C6H5 + CH3C+O → C6H5COCH3
For the following bond cleavages, use curved-arrows to show the electron flow and classify each as homolysis or heterolysis. Identify reactive intermediate produced as free radical, carbocation and carbanion.
Which of the following represents the correct IUPAC name for the compounds concerned?
(a) 2,2-Dimethylpentane or 2-Dimethylpentane
(b) 2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane
(c) 2-Chloro-4-methylpentane or 4-Chloro-2-methylpentane
(d) But-3-yn-1-ol or But-4-ol-1-yne
Draw the resonance structures for the following compounds. Show the electron shift using curved-arrow notation.
(a) C6H5OH
(b) C6H5NO2
(c) CH3CH=CHCHO
(d) C6H5–CHO
(e) C6 H5 - C+H2
(f) CH3CH = CHC+H2
Which of the following carbocation is most stable ?
How do you account for the formation of ethane during chlorination of methane?
What will be the minimum pressure required to compress 500 dm3 of air at 1 bar to 200 dm3 at 30°C?
What are the common physical and chemical features of alkali metals?
Calculate the molecular mass of the following:
(i) H2O
(ii) CO2
(iii) CH4
Assign oxidation number to the underlined elements in each of the following species:
(a) NaH2PO4
(b) NaHSO4
(c) H4P2O7
(d) K2MnO4
(e) CaO2
(f) NaBH4
(g) H2S2O7
(h) KAl(SO4)2.12 H2O
What is the basic theme of organisation in the periodic table?
Explain the formation of a chemical bond.
Choose the correct answer. A thermodynamic state function is a quantity
(i) used to determine heat changes
(ii) whose value is independent of path
(iii) used to determine pressure volume work
(iv) whose value depends on temperature only.
A liquid is in equilibrium with its vapour in a sealed container at a fixed temperature. The volume of the container is suddenly increased.
a) What is the initial effect of the change on vapour pressure?
b) How do rates of evaporation and condensation change initially?
c) What happens when equilibrium is restored finally and what will be the final vapour pressure?
Justify the position of hydrogen in the periodic table on the basis of its electronic configuration.
For the reaction at 298 K,
2A + B → C
ΔH = 400 kJ mol-1and ΔS = 0.2 kJ K-1mol-1
At what temperature will the reaction become spontaneous considering ΔH and ΔS to be constant over the temperature range?
How many electrons in an atom may have the following quantum numbers?
(a) n = 4,
(b) n = 3, l = 0
Pay load is defined as the difference between the mass of displaced air and the mass of the balloon. Calculate the pay load when a balloon of radius 10 m, mass 100 kg is filled with helium at 1.66 bar at 27°C. (Density of air = 1.2 kg m–3 and R = 0.083 bar dm3 K–1 mol–1).
What is the equilibrium concentration of each of the substances in the equilibrium when the initial concentration of ICl was 0.78 M ?
2ICl (g) ↔ I2 (g) + Cl2 (g); Kc = 0.14
Addition of HBr to propene yields 2-bromopropane, while in the presence of benzoyl peroxide, the same reaction yields 1-bromopropane. Explain and give mechanism.
Saline hydrides are known to react with water violently producing fire. Can CO2, a well known fire extinguisher, be used in this case? Explain.
Define electronegativity. How does it differ from electron gain enthalpy?
Aluminium trifluoride is insoluble in anhydrous HF but dissolves on addition of NaF. Aluminium trifluoride precipitates out of the resulting solution when gaseous BF3 is bubbled through. Give reasons.
Starting with sodium chloride how would you proceed to prepare
(i) sodium metal (ii) sodium hydroxide (iii) sodium peroxide (iv) sodium carbonate?
Why does the following reaction occur ?
XeO4– 6(aq) + 2F – (aq) + 6H + (aq) → XeO3(g) + F2(g) + 3H2O(l)
What conclusion about the compound Na4XeO6 (of which XeO4– 6 is a part) can be drawn from the reaction.