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
Inductive effect
The permanent displacement of sigma electrons along a saturated chain, whenever an electron withdrawing or electron donating group is present, is called inductive effect.
Inductive effect could be + I effect or - I effect. When an atom or group attracts electrons towards itself more strongly than hydrogen, it is said to possess - I effect. For example,
F —← CH2 —← CH2 —← CH2 —←CH3
When an atom or group of atoms attracts electrons towards itself less strongly than hydrogen, it is said to possess + I effect. For example,
CH3 —→ CH2 →→ -Cl
Electrometric effect
It involves the complete transfer of the shared pair of π-electrons to either of the two atoms linked by multiple bonds in the presence of an attacking agent. For example,
Electrometric effect could be + E effect or - E effect.
+ E effect: When the electrons are transferred towards the attacking reagent
- E effect: When the electrons are transferred away from the attacking reagent
(a) Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
The order of acidity can be explained on the basis of Inductive effect (- I effect). As the number of chlorine atoms increases, the - I effect increases. With the increase in - I effect, the acid strength also increases accordingly.
(b) CH3CH2COOH > (CH3)2 CHCOOH > (CH3)3 C.COOH
The order of acidity can be explained on the basis of inductive effect (+ I effect). As the number of alkyl groups increases, the + I effect also increases. With the increase in + I effect, the acid strength also increases accordingly.
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
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 ?
What is the relationship between the members of following pairs of structures? Are they structural or geometrical isomers or resonance contributors?
(a)
(b)
(c)
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.
Yellow light emitted from a sodium lamp has a wavelength (λ) of 580 nm. Calculate the frequency (ν) and wave number () of the yellow light.
The mass of an electron is 9.1 × 10–31 kg. If its K.E. is 3.0 × 10–25 J, calculate its wavelength.
The first (ΔiH1) and the second (ΔiH) ionization enthalpies (in kJ mol–1) and the (ΔegH) electron gain enthalpy (in kJ mol–1) of a few elements are given below:
Elements | ΔiH1 | ΔiH | ΔegH |
I | 520 | 7300 | -60 |
II | 419 | 3051 | -48 |
III | 1681 | 3374 | -328 |
IV | 1008 | 1846 | -295 |
V | 2372 | 5251 | +48 |
VI | 738 | 1451 | -40 |
Which of the above elements is likely to be :
(a) the least reactive element.
(b) the most reactive metal.
(c) the most reactive non-metal.
(d) the least reactive non-metal.
(e) the metal which can form a stable binary halide of the formula MX2, (X=halogen).
(f) the metal which can form a predominantly stable covalent halide of the formula MX (X=halogen)?
The size of isoelectronic species — F–, Ne and Na+ is affected by
(a) Nuclear charge (Z )
(b) Valence principal quantum number (n)
(c) Electron-electron interaction in the outer orbitals
(d) None of the factors because their size is the same.
Use Lewis symbols to show electron transfer between the following atoms to form cations and anions:
(a) K and S (b) Ca and O (c) Al and N.
Compare the relative stability of the following species and indicate their magnetic properties:
O2,O2+,O2- (superoxide), O22-(peroxide)
For the following equilibrium, Kc = 6.3 × 1014 at 1000 K
NO (g) + O3 (g) ↔ NO2 (g) + O2 (g)
Both the forward and reverse reactions in the equilibrium are elementary bimolecular reactions. What is Kc, for the reverse reaction?
Calculate the wavelength, frequency and wave number of a light wave whose period is 2.0 × 10–10 s.
For the reaction, 2Cl(g) → Cl2(g),what are the signs of ΔH and ΔS ?
Consider the reactions:
(a) 6CO2(g) + 6H2O(l) → C6H12O6(aq) + 6O2(g)
(b) O3(g) + H2O2(l) → H2O(l) + 2O2(g)
Why it is more appropriate to write these reactions as:
(a) 6CO2(g) + 12H2O(l) → C6H12O6(aq) + 6H2O(l) + 6O2(g)
(b) O3(g) + H2O2(l) → H2O(l) + O2(g) + O2(g)
Also suggest a technique to investigate the path of the above (a) and (b) redox reactions.