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.
When metal X is treated with sodium hydroxide, a white precipitate (A) is obtained, which is soluble in excess of NaOH to give soluble complex (B). Compound (A) is soluble in dilute HCl to form compound (C). The compound (A) when heated strongly gives (D), which is used to extract metal. Identify (X), (A), (B), (C) and (D). Write suitable equations to support their identities.
What properties of water make it useful as a solvent? What types of compound can it (i) dissolve, and (ii) hydrolyse?
For the reaction, 2Cl(g) → Cl2(g),what are the signs of ΔH and ΔS ?
Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4 Cl(g)
and calculate bond enthalpy of C – Cl in CCl4(g).
ΔvapH0(CCl4) = 30.5 kJ mol–1.
ΔfH0 (CCl4) = –135.5 kJ mol–1.
ΔaH0 (C) = 715.0 kJ mol–1 , where ΔaH0 is enthalpy of atomisation
ΔaH0 (Cl2) = 242 kJ mol–1
The bromine atom possesses 35 electrons. It contains 6 electrons in 2p orbital, 6 electrons in 3p orbital and 5 electrons in 4p orbital. Which of these electron experiences the lowest effective nuclear charge?
Although both CO2 and H2O are triatomic molecules, the shape of H2O molecule is bent while that of CO2 is linear. Explain this on the basis of dipole moment.
A welding fuel gas contains carbon and hydrogen only. Burning a small sample of it in oxygen gives 3.38 g carbon dioxide, 0.690 g of water and no other products. A volume of 10.0 L (measured at STP) of this welding gas is found to weigh 11.6 g. Calculate
(i) empirical formula,
(ii) molar mass of the gas, and
(iii) molecular formula.
What is the SI unit of mass? How is it defined?
What is smog? How is classical smog different from photochemical smog?
What is the total number of sigma and pi bonds in the following molecules?
(a) C2H2 (b) C2H4