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.
Emission transitions in the Paschen series end at orbit n = 3 and start from orbit n and can be represented as v = 3.29 × 1015 (Hz) [1/32 – 1/n2]
Calculate the value of n if the transition is observed at 1285 nm. Find the region of the spectrum.
Explain why is there a phenomenal decrease in ionisation enthalpy from carbon to silicon?
Why are potassium and cesium, rather than lithium used in photoelectric cells?
Arrange the following
(i) CaH2, BeH2 and TiH2 in order of increasing electrical conductance.
(ii) LiH, NaH and CsH in order of increasing ionic character.
(iii) H-H, D-D and F-F in order of increasing bond dissociation enthalpy.
(iv) NaH, MgH2 and H2O in order of increasing reducing property.
Why are lithium salts commonly hydrated and those of the other alkali metal ions usually anhydrous?
What is the number of photons of light with a wavelength of 4000 pm that provide 1 J of energy?
Balance the following redox reactions by ion – electron method :
(a) MnO4 – (aq) + I – (aq) → MnO2 (s) + I2(s) (in basic medium)
(b) MnO4 – (aq) + SO2 (g) → Mn2+ (aq) + HSO4– (aq) (in acidic solution)
(c) H2O2 (aq) + Fe 2+ (aq) → Fe3+ (aq) + H2O (l) (in acidic solution)
(d) Cr2O7 2– + SO2(g) → Cr3+ (aq) + SO42– (aq) (in acidic solution)
Do you expect different products in solution when aluminium(III) chloride and potassium chloride treated separately with
(i) normal water
(ii) acidified water, and
(iii) alkaline water?
Write equations wherever necessary.
The pH of milk, black coffee, tomato juice, lemon juice and egg white are 6.8, 5.0, 4.2, 2.2 and 7.8 respectively. Calculate corresponding hydrogen ion concentration in each.
What will be the pressure of the gaseous mixture when 0.5 L of H2 at 0.8 bar and 2.0 L of dioxygen at 0.7 bar are introduced in a 1L vessel at 27°C?