Discuss the principle of estimation of halogens, sulphur and phosphorus present in an organic compound.
Estimation of halogens
Halogens are estimated by the Carius method. In this method, a known quantity of organic compound is heated with fuming nitric acid in the presence of silver nitrate, contained in a hard glass tube called the Carius tube, taken in a furnace. Carbon and hydrogen that are present in the compound are oxidized to form CO2 and H2O respectively and the halogen present in the compound is converted to the form of AgX. This AgX is then filtered, washed, dried, and weighed.
Let the mass of organic compound be m g.
Mass of AgX formed = m1 g
1 mol of Agx contains 1 mol of X.
Therefore, Mass of halogen in m1 g of AgX = (Atomic mass of X x m1 g) / (Molecular mass of AgX)
Thus, % of halogen will be = (Atomic mass of X x m1 x 100) / (Molecular mass of AgX x m)
Estimation of Sulphur
In this method, a known quantity of organic compound is heated with either fuming nitric acid or sodium peroxide in a hard glass tube called the Carius tube. Sulphur, present in the compound, is oxidized to form sulphuric acid. On addition of excess of barium chloride to it, the precipitation of barium sulphate takes place. This precipitate is then filtered, washed, dried, and weighed.
Let the mass of organic compound be m g.
Mass of BaSO4 formed = m1 g
1 mol of BaSO4 = 233 g BaSO4 = 32 g of Sulphur
Therefore, m1 g of BaSO4 contains 32 x m1 / 233 g of sulphur
Thus, percentage of sulphur = 32 x m1 x100 / 233 x m
Estimation of phosphorus
In this method, a known quantity of organic compound is heated with fuming nitric acid. Phosphorus, present in the compound, is oxidized to form phosphoric acid. By adding ammonia and ammonium molybdate to the solution, phosphorus can be precipitated as ammonium phosphomolybdate.
Phosphorus can also be estimated by precipitating it as MgNH4PO4 by adding magnesia mixture, which on ignition yields Mg2P2O7.
Let the mass of organic compound be m g.
Mass of ammonium phosphomolybdate formed = m1 g
Molar mass of ammonium phosphomolybdate = 1877 g
Thus, percentage of phosphorus = (31 x m1 x 100 %) / (1877 x m)
If P is estimated as Mg2P2O7,
Then percentage of phosphorus = (62xm1x100%) / (222xm)
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.
If the photon of the wavelength 150 pm strikes an atom and one of its inner bound electrons is ejected out with a velocity of 1.5 × 107 ms–1, calculate the energy with which it is bound to the nucleus.
The Mn3+ ion is unstable in solution and undergoes disproportionation to give Mn2+, MnO2, and H+ ion. Write a balanced ionic equation for the reaction.
Write the expression for the equilibrium constant, Kc for each of the following reactions:
(i) 2NOCl (g) ↔ 2NO (g) + Cl2 (g)
(ii) 2Cu(NO3)2 (s) ↔ 2CuO (s) + 4NO2 (g) + O2 (g)
(iii) CH3COOC2H5(aq) + H2O(l) ↔ CH3COOH (aq) + C2H5OH (aq)
(iv) Fe3+ (aq) + 3OH– (aq) ↔ Fe(OH)3 (s)
(v) I2 (s) + 5F2 ↔ 2IF5
Apart from tetrahedral geometry, another possible geometry for CH4 is square planar with the four H atoms at the corners of the square and the C atom at its centre. Explain why CH4 is not square planar?
Calculate the wave number for the longest wavelength transition in the Balmer series of atomic hydrogen.
Predict which of the following reaction will have appreciable concentration of reactants and products:
a) Cl2 (g) ↔ 2Cl (g) Kc = 5 ×10–39
b) Cl2 (g) + 2NO (g) ↔ 2NOCl (g) Kc = 3.7 × 108
c) Cl2 (g) + 2NO2 (g) ↔ 2NO2Cl (g) Kc = 1.8
Define hydrogen bond. Is it weaker or stronger than the van der Waals forces?
Energy of an electron in the ground state of the hydrogen atom is –2.18 × 10–18 J. Calculate the ionization enthalpy of atomic hydrogen in terms of J mol–1.
Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO3 with silver electrodes
(ii) An aqueous solution AgNO3 with platinum electrodes
(iii) A dilute solution of H2SO4 with platinum electrodes
(iv) An aqueous solution of CuCl2 with platinum electrodes.
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)?