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.
Propanal and pentan-3-one are the ozonolysis products of an alkene? What is the structural formula of the alkene?
Predict the formula of the stable binary compounds that would be formed by the combination of the following pairs of elements. (a) Lithium and oxygen
(b) Magnesium and nitrogen
(c) Aluminium and iodine
(d) Silicon and oxygen
(e) Phosphorus and fluorine
(f) Element 71 and fluorine
The ionization constant of nitrous acid is 4.5 x 10-4. Calculate the pH of 0.04 M sodium nitrite solution and also its degree of hydrolysis.
Write balanced equations for reactions between
(a) Na2O2and water
(b) KO2 and water
(c) Na2O and CO2
For the process to occur under adiabatic conditions, the correct condition is:
(i) ΔT = 0
(ii) Δp = 0
(iii) q = 0
(iv) w = 0
Define environmental chemistry.
What does atomic radius and ionic radius really mean to you?
Describe the theory associated with the radius of an atom as it
(a) gains an electron
(b) loses an electron
At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO2 in equilibrium with soild carbon has 90.55% CO by mass
C (s) + CO2 (g) ↔ 2CO (g)
Calculate Kc for this reaction at the above temperature.
Anything that influences the valence electrons will affect the chemistry of the element. Which one of the following factors does not affect the valence shell?
(a) Valence principal quantum number (n)
(b) Nuclear charge (Z)
(c) Nuclear mass
(d) Number of core electrons.