Differentiate between the principle of estimation of nitrogen in an organic compound by
(i) Dumas method and
(ii) Kjeldahl's method.
In Dumas method, a known quantity of nitrogen containing organic compound is heated strongly with excess of copper oxide in an atmosphere of carbon dioxide to produce free nitrogen in addition to carbon dioxide and water. The chemical equation involved in the process can be represented as
The traces of nitrogen oxides can also be produced in the reaction, which can be reduced to dinitrogen by passing the gaseous mixture over a heated copper gauge. The dinitrogen produced is collected over an aqueous solution of potassium hydroxide. The volume of nitrogen produced is then measured at room temperature and atmospheric pressure.
On the other hand, in Kjeldahl's method, a known quantity of nitrogen containing organic compound is heated with concentrated sulphuric acid. The nitrogen present in the compound is quantitatively converted into ammonium sulphate. It is then distilled with excess of sodium hydroxide. The ammonia evolved during this process is passed into a known volume of H2SO4. The chemical equations involved in the process are
The acid that is left unused is estimated by volumetric analysis (titrating it against a standard alkali) and the amount of ammonia produced can be determined. Thus, the percentage of nitrogen in the compound can be estimated. This method cannot be applied to the compounds, in which nitrogen is present in a ring structure, and also not applicable to compounds containing nitro and azo groups.
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.
On the basis of quantum numbers, justify that the sixth period of the periodic table should have 32 elements.
Compare the relative stability of the following species and indicate their magnetic properties:
O2,O2+,O2- (superoxide), O22-(peroxide)
What is meant by hybridisation of atomic orbitals? Describe the shapes of sp, sp2, sp3 hybrid orbitals.
Among NH3, H2O and HF, which would you expect to have highest magnitude of hydrogen bonding and why?
Balance the following equations in basic medium by ion-electron method and oxidation number methods and identify the oxidising agent and the reducing agent.
(a) P4(s) + OH – (aq) → PH3(g) + HPO2 – (aq)
(b) N2H4(l) + ClO3 – (aq) → NO(g) + Cl–(g)
(c) Cl2O7 (g) + H2O2(aq) → ClO – 2(aq) + O2(g) + H + (aq)
Pressure of 1 g of an ideal gas A at 27 °C is found to be 2 bar. When 2 g of another ideal gas B is introduced in the same flask at same temperature the pressure becomes 3 bar. Find a relationship between their molecular masses.
Find out the value of Kc for each of the following equilibria from the value of Kp:
(i) 2NOCl (g) ↔ 2NO (g) + Cl2 (g); Kp = 1.8 × 10–2 at 500 K
(ii) CaCO3 (s) ↔ CaO(s) + CO2(g); Kp = 167 at 1073 K
What is the state of hybridisation of carbon in
(a) CO2-3
(b) diamond
(c) graphite?
Suggest the name of a Lewis acid other than anhydrous aluminium chloride which can be used during ethylation of benzene.
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