Two gas-phase ion-molecule reaction systems are presented here based on measurements done in a temperature variable 22-pole trapping machine. In the first case, the proton affinity of methane is determined based on a new technique for measuring the equilibrium constant of the HCO2+ + CH4 <=> CH5+ + CO2 reaction. The second case reports to the (Ar + N2 )+ reaction system, with reaction rate temperature dependencies measurements made both in the forward and reverse direction with different and complementary methods. The temperature variable 22-pole trapping machine allows one to determine equilibrium constants and reaction rate coefficients over a wide range of temperatures. The coupling of an effusive beam to the setup overcomes the problem of neutral gas wall condensation and extends the temperature range measurements beyond condensation point. The introduction (Chapter 1) gives a short overview about the rf technology and parallel experimental techniques developed in order to better characterize and understand the several mechanisms related to ion-molecule reactions. It also focuses some aspects of reaction rate temperature dependencies determination as well as thermodynamical equilibrium in laboratory environment. A short description of the setup and experimental methods are presented in Chapter 2. Based on equilibrium constant measurements, Chapter 3 is dedicated to the proton affinity of methane. This concept has applications on several fields such as atmospheric and combustion modelling, or testing empirical and ab initio theories for electronic structures. The (Ar − N2 )+ system presented in Chapter 4, is known for being a good case study for inferring the role of vibrational excitation in reaction dynamics and to the existence of non-adiabatic coupling. The experimental results here presented for the N2+ + Ar reaction demonstrate that it is possible to avoid parallel reactions with first vibrational excited state of nitrogen (N2 (ν = 1)). On the other hand, the reverse reaction experiments confirm the existence of a minimum of the reaction rate in the 30 to 300 K range, due to the existence of two reaction channels. The question of the high rate coefficient towards lower temperatures being related to the N2 rotational ground state population is raised. A summary and outlook are presented in Chapter 5, where some new possible paths of investigation are pointed out.

Two gas-phase ion-molecule reaction systems are presented here based on measurements done in a temperature variable 22-pole trapping machine. In the first case, the proton affinity of methane is determined based on a new technique for measuring the equilibrium constant of the HCO2+ + CH4 <=> CH5+ + CO2 reaction. The second case reports to the (Ar + N2 )+ reaction system, with reaction rate temperature dependencies measurements made both in the forward and reverse direction with different and complementary methods. The temperature variable 22-pole trapping machine allows one to determine equilibrium constants and reaction rate coefficients over a wide range of temperatures. The coupling of an effusive beam to the setup overcomes the problem of neutral gas wall condensation and extends the temperature range measurements beyond condensation point. The introduction (Chapter 1) gives a short overview about the rf technology and parallel experimental techniques developed in order to better characterize and understand the several mechanisms related to ion-molecule reactions. It also focuses some aspects of reaction rate temperature dependencies determination as well as thermodynamical equilibrium in laboratory environment. A short description of the setup and experimental methods are presented in Chapter 2. Based on equilibrium constant measurements, Chapter 3 is dedicated to the proton affinity of methane. This concept has applications on several fields such as atmospheric and combustion modelling, or testing empirical and ab initio theories for electronic structures. The (Ar − N2 )+ system presented in Chapter 4, is known for being a good case study for inferring the role of vibrational excitation in reaction dynamics and to the existence of non-adiabatic coupling. The experimental results here presented for the N2+ + Ar reaction demonstrate that it is possible to avoid parallel reactions with first vibrational excited state of nitrogen (N2 (ν = 1)). On the other hand, the reverse reaction experiments confirm the existence of a minimum of the reaction rate in the 30 to 300 K range, due to the existence of two reaction channels. The question of the high rate coefficient towards lower temperatures being related to the N2 rotational ground state population is raised. A summary and outlook are presented in Chapter 5, where some new possible paths of investigation are pointed out.

(Résumé de la thèse) Ayant constaté l’échec de ses Objectifs 2010 pour la biodiversité, dont, entre autres, l’incapacité de l’Empreinte écologique à rendre compte de la biodiversité, la Convention sur la Diversité Biologique a adopté en 2011 "Les objectifs d’Aichi (2011-2020) pour la biodiversité". Parmi ceux-ci les objectifs 1 et 2 concernent la prise de conscience des valeurs de la biodiversité, leur intégration dans les processus de planification nationaux et locaux de développement, et leur incorporation dans les comptabilités nationales. Ce en quoi ces objectifs de la CDB convergent désormais avec ceux des Nations Unies concernant le Système de Comptabilité Economique et Environnementale (SCEE). La présente thèse s’inscrit dans ce cadre de questionnement unifié. Elle a le double objectif : (a) de rechercher, fonder et mettre au point une unité de mesure biophysique de la diversité biologique caractérisant tout aussi bien l’ordre naturel que le désordre anthropogénique, et (b) d’incorporer celle-ci dans un nouveau système de comptabilité physique, le Bilan écologique. Celui-ci est susceptible de comparer, à toutes échelles territoriales, le Passif écologique des collectivités urbaines, vu comme le reflet biophysique de leur comptabilité monétaire, à l’Actif écologique de leurs espaces naturels, afin de révéler les relations de cause à effet, et de signifier les impacts cumulés de la perturbation anthropogénique sur l’Ecosphère et la Biosphère. Il aurait ainsi vocation, à terme, à nous permettre de caractériser les voies d’un développement véritablement écologique des territoires. / (Abstract of the thesis) Having noted the failure of its 2010 targets for biodiversity, including, among others, the inability of the Ecological Footprint to account for biodiversity, the Convention on Biological Diversity adopted in 2011 "The 2011-2020 Aichi Targets for biodiversity". Among these, objectives 1 and 2 concern awareness of the values of biodiversity, their integration into national and local development planning process, and their incorporation into national accounts. This how these objectives of the CBD converge now with those of the United Nations for the System of Environmental-Economic Accounting (SEEA). This thesis lie within this unified questioning framework. It has the double purpose : (a) of searching for, founding and developing a biophysical measurement unit of biodiversity, characterizing just as well the natural order as the anthropogenic disorder, and (b) to incorporate it into a new physical accounting system, the Ecological balance sheet. The latter is likely to compare, for all territorial scales, the Ecological liability of urban communities, seen as the biophysical reflection of their monetary accounting, to the Ecological asset of their natural spaces, in order to reveal the relationships of cause and effect, and to signify the cumulative impacts of anthropogenic disturbance on the Ecosphere and the Biosphere. In the end, it would have so vocation to enable us to characterize the ways of a truly ecological development of the territories.