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.
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).
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?
What are the various factors due to which the ionization enthalpy of the main group elements tends to decrease down a group?
Out of benzene, m-dinitrobenzene and toluene which will undergo nitration most easily and why?
In astronomical observations, signals observed from the distant stars are generally weak. If the photon detector receives a total of 3.15 × 10–18 J from the radiations of 600 nm, calculate the number of photons received by the detector.
Write the resonance structures for SO3, NO2 and .
The enthalpies of all elements in their standard states are:
(i) unity
(ii) zero
(iii) < 0
(iv) different for each element
How much energy is required to ionise a H atom if the electron occupies n = 5 orbit? Compare your answer with the ionization enthalpy of H atom (energy required to remove the electron from n =1 orbit).
Calculate the amount of carbon dioxide that could be produced when
(i) 1 mole of carbon is burnt in air.
(ii) 1 mole of carbon is burnt in 16 g of dioxygen.
(iii) 2 moles of carbon are burnt in 16 g of dioxygen.
Calculate a) ΔG0 and b) the equilibrium constant for the formation of NO2 from NO and O2 at 298K
NO (g) + ½ O2 (g) ↔ NO2 (g)
where ΔfG0 (NO2) = 52.0 kJ/mol
ΔfG0 (NO) = 87.0 kJ/mol
ΔfG0 (O2) = 0 kJ/mol