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.
If the position of the electron is measured within an accuracy of + 0.002 nm, calculate the uncertainty in the momentum of the electron. Suppose the momentum of the electron is h/4πm × 0.05 nm, is there any problem in defining this value.
(i) Calculate the total number of electrons present in one mole of methane.
(ii) Find
(a) the total number and
(b) the total mass of neutrons in 7 mg of 14C. (Assume that mass of a neutron = 1.675 × 10–27 kg).
(iii) Find
(a) the total number and
(b) the total mass of protons in 34 mg of NH3 at STP.
Will the answer change if the temperature and pressure are chang
What is the basic difference between the terms electron gain enthalpy and electronegativity?
If 0.561 g of KOH is dissolved in water to give 200 mL of solution at 298 K. Calculate the concentrations of potassium, hydrogen and hydroxyl ions. What is its pH?
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).
H3PO3 can be represented by structures 1 and 2 shown below. Can these two structures be taken as the canonical forms of the resonance hybrid representing H3PO3? If not, give reasons for the same.
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.
What happens when
(i) sodium metal is dropped in water ?
(ii) sodium metal is heated in free supply of air ?
(iii) sodium peroxide dissolves in water ?
How would you explain the lower atomic radius of Ga as compared to Al?
Describe the theory associated with the radius of an atom as it
(a) gains an electron
(b) loses an electron