Structure & Reactivity in Organic, Biological and Inorganic Chemistry by Chris Schaller is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported License.
Reactivity in Chemistry
Nitrogen Reduction
NF1. Introduction to Nitrogen Reduction
Nitrogen is the most abundant element in earth's atmosphere. It makes up about 80% of the air around us. It is also a key component of biomolecules. Nitrogen contributes a crucial part of amino acids, which in turn make up proteins, which are the cell's machinery. Nitrogen also provides a crucial part of DNA, which transmits our genetic code and governs the expression of those proteins. Although less well known, many nitrogen-containing natural products such as alkaloids play important roles in biology.
Getting that nitrogen out of the air and into the cell is a Herculean task. Nitrogen in the air is present in its elemental form, which is diatomic nitrogen or dinitrogen, N2. The nitrogen in biomolecules is always found individually; it is always bound to other atoms, especially carbon and hydrogen, but never to other nitrogens. That means the two nitrogen atoms in dinitrogen atom have to be cleaved apart so that they can be combined with other atoms in these useful molecules. That's a problem. N2 is exceptionally stable. Breaking the bond between the two nitrogen atoms costs about 225 kcal/mol. Most of the other bonds in the universe are not nearly so strong.
So how do we break that incredibly strong bond and combine it with other atoms to make molecules? For most of our history, we didn't (we being people). Neither could other animals. Neither could plants. Microbes could do it all along, though.
Certain bacteria, called diazotrophs, contain an enzyme called nitrogenase that can catalytically convert dinitrogen to ammonia. Some diazotrophs, called rhizobacteria, have a symbiotic relationship with specific kinds of plant roots. They provide ammonia or amino acids to the plant and the plant provides them with organic compounds such as malate that can be metabolised to obtain energy.
N2 + 6 H+ + 6 e- → 2 NH3
All plants need nitrogen to grow, but by evolving to have this symbiotic relationship with rhizobacteria, legume plants have found a distinct advantage over others.
Other bacteria actually live on ammonia. They use it for metabolism the way other organisms use carbohydrates. In doing so, they oxidise the ammonia to nitrites the way other organisms oxidise carbohydrates to carbon dioxide.
NH3 + O2 → NO2- + 3 H+ + 2 e-
There are even bacteria that oxidise the nitrites.
2 NO2- + O2 → 2 NO3-
Problem NF1.1.
Calculate the oxidation state of nitrogen in each of the following compounds.
a) N2 b) NH3 c) NH4+ d) NO2- d) NO3-
Problem NF2.2.
The oxidation of nitrite must involve electron transfer. Identify:
a) the oxidant
b) the reductant
c) the number of electrons transferred from reductant to oxidant
All of these compounds -- ammonia, nitrites, and nitrates -- can be used by plants as sources of nitrogen. People, who have been farming for thousands of years, have developed a number of methods of making sure their crops had plenty of these nutrients available. There are familiar stories of different Native American groups planting corn and squash along with rhizobacter-nurturing beans. In South America, Andean farmers collected guano for their fields.
At the turn of the twentieth century, a great leap forward came with the discovery that ammonia could be manufactured directly from nitrogen on a massive scale. This technology, called the Haber-Bosch process, is responsible for a significant portion of the nitrogen found in food.
The focus of this chapter is on the processes that have allowed the cleavage of the nitrogen bond, by both biological and industrial means.
See the section on nitrogenase at Henry Jakubowski's Biochemistry Online.
This site was written by Chris P. Schaller, Ph.D., College of Saint Benedict / Saint John's University (retired) with contributions from other authors as noted. It is freely available for educational use.
Structure & Reactivity in Organic, Biological and Inorganic Chemistry by Chris Schaller is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported License.
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