Skip to content

Chemistry · Ch 14 — The p-Block Elements

Dinitrogen

14.2

Dinitrogen

Preparation

Dinitrogen is manufactured on an industrial scale by liquefying air and then separating it by fractional distillation: liquid nitrogen, which boils at the lower temperature of 77.2 K, distils off first, leaving liquid oxygen (b.p. 90 K) behind.

In the laboratory, a convenient route is to treat an aqueous solution of ammonium chloride with sodium nitrite:

NH4Cl(aq)+NaNO2(aq)→N2(g)+2H2O(l)+NaCl(aq)NH_4Cl(aq) + NaNO_2(aq) \rightarrow N_2(g) + 2H_2O(l) + NaCl(aq)

This reaction also throws off small amounts of NONO and HNO3HNO_3 as impurities, which can be scrubbed out by bubbling the gas through aqueous sulphuric acid containing potassium dichromate. Dinitrogen can equally well be obtained from the thermal decomposition of ammonium dichromate:

(NH4)2Cr2O7→HeatN2+4H2O+Cr2O3(NH_4)_2Cr_2O_7 \xrightarrow{\text{Heat}} N_2 + 4H_2O + Cr_2O_3

For a much purer sample, the thermal decomposition of sodium or barium azide is used, for example:

Ba(N3)2→Ba+3N2Ba(N_3)_2 \rightarrow Ba + 3N_2

Properties

Dinitrogen is a colourless, odourless, tasteless and non-toxic gas, and its nitrogen atoms occur naturally as two stable isotopes, 14N^{14}N and 15N^{15}N. It dissolves only sparingly in water (23.2 cm3^3 per litre of water at 273 K and 1 bar) and, in keeping with its weak intermolecular forces, has low freezing and boiling points (see Table 7.1).

At room temperature N2N_2 is quite unreactive, a direct consequence of the very high bond enthalpy of its N≡NN\equiv N triple bond — but its reactivity rises sharply as the temperature is increased. At elevated temperature it will combine directly with certain metals to give predominantly ionic nitrides, and with non-metals to give covalent nitrides, for instance:

6Li+N2→Heat2Li3N6Li + N_2 \xrightarrow{\text{Heat}} 2Li_3N

3Mg+N2→HeatMg3N23Mg + N_2 \xrightarrow{\text{Heat}} Mg_3N_2

Around 773 K, and in the presence of a catalyst, dinitrogen combines with hydrogen in the industrially vital Haber process to give ammonia:

N2(g)+3H2(g)⇌773 K2NH3(g);ΔfH∘=−46.1 kJ mol−1N_2(g) + 3H_2(g) \underset{773\ K}{\rightleftharpoons} 2NH_3(g); \quad \Delta_fH^\circ = -46.1\ \text{kJ mol}^{-1}

Dinitrogen only reacts with dioxygen at very high temperature — around 2000 K — to give nitric oxide:

N2+O2(g)→Heat2NO(g)N_2 + O_2(g) \xrightarrow{\text{Heat}} 2NO(g) …