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.
In Milikan’s experiment, static electric charge on the oil drops has been obtained by shining X-rays.
If the static electric charge on the oil drop is –1.282 × 10–18C, calculate the number of electrons present on it.
In Rutherford’s experiment, generally the thin foil of heavy atoms, like gold, platinum etc. have been used to be bombarded by the α-particles. If the thin foil of light atoms like aluminium etc. is used, what difference would be observed from the above results?
The increasing order of reactivity among group 1 elements is Li < Na < K < Rb CI > Br > I. Explain.
The pH of 0.1M solution of cyanic acid (HCNO) is 2.34. Calculate the ionization constant of the acid and its degree of ionization in the solution.
Draw the cis and trans structures of hex-2-ene. Which isomer will have higher b.p. and why?
Among NH3, H2O and HF, which would you expect to have highest magnitude of hydrogen bonding and why?
Calculate the molarity of a solution of ethanol in water in which the mole fraction of ethanol is 0.040 (assume the density of water to be one).
Equilibrium constant, Kc for the reaction
N2 (g) + 3H2 (g) ↔ 2NH3 (g) at 500 K is 0.061
At a particular time, the analysis shows that composition of the reaction mixture is 3.0 mol L–1 N2, 2.0 mol L–1 H2 and 0.5 mol L–1 NH3.
Is the reaction at equilibrium?
If not in which direction does the reaction tend to proceed to reach equilibrium?
Define the bond length.
Dinitrogen and dihydrogen react with each other to produce ammonia according to the following chemical equation:
N2(g) + H2(g) → 2NH3(g)
(i) Calculate the mass of ammonia produced if 2.00 × 103 g dinitrogen reacts with 1.00 × 103 g of dihydrogen.
(ii) Will any of the two reactants remain unreacted?
(iii) If yes, which one and what would be its mass?