Primitive Analyses

In later chapters, much of our attention will focus on analyzing how a system responds to a process. The primitive stages of an analysis lead to a sketch or diagram that helps us visualize the system and the processes acting on it. We divide such sketches into two general classes one for closed systems ( 1.4.1), the other for open systems ( 1.4.2). For closed systems, no further primitive concepts apply, and a thermodynamic analysis proceeds as described in Chapter 2. But for open systems, the sketch can be enhanced by invoking one additional primitive concept equations that represent system inventories. These equations are discussed in 1.4.2. 

In general the stuff equation is a differential equation and its accumulation term can be positive, negative, or zero that is, the amount of stuff in the system may increase, decrease, or remain constant with time. In a particular situation several kinds of stuff may need to be inventoried examples include molecules, energy, and entropy. 

The stuff equation applies to both conserved and non-conserved quantities. Conserved quantities can be neither created nor destroyed so, for such quantities the stuff equation reduces to a general conservation principle 

One important conservation principle is provided by molecular theory atoms are conserved parcels of matter. (We ignore subatomic processes such as fission or fusion and consider only changes that do not modify the identities of atoms.) At the macroscopic level this conservation principle is the mass or material balance 

instead of total material, the inventory is to be conducted on chemical species (moles), then (1.4.3) continues to apply, so long as chemical reactions are not occurring. If reactions occur, then mole numbers may change and (1.4.1) would apply rather than (1.4.3). So, in the absence of nuclear processes, mass is always conserved, but moles are generally conserved only in the absence of chemical reactions. 

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These concepts are so basic that we call them primitives, for everything in later chapters builds on these ideas. You have probably encountered this material before, but our presentation may be new to you. The chapter is divided into primitive things ( 1.1), primitive quantities ( 1.2), primitive changes ( 1.3), and primitive analyses ( 1.4). 

Characterization of the reaction intermediate is facilitated by studies in a flow system in which the sample cell and a reference cell are mounted in series in a double beam spectrometer (IS). Not only can we observe the intermediate bands under rigorous steady state conditions, but we can monitor the conversion by sampling the effluent. In addition, the reference cell assures the spectrum we see is that of surface species. Primitive analysis of the kinetics reveals the intermediate is favored by relatively high ethylene pressures hence, use of a reference cell to cancel contributions of the gas phase is an important factor. 

When processes are applied to closed systems, we can usually identify the system state at two or more different times. The diagrams in Figure 1.4 and schematics in Figure 1.5 are of this type in those examples, we know the initial and final states of the system. Intermediate states may be knowable (reversible) or unknowable (irreversible) nevertheless, the identities of two states may be sufficient to allow us to analyze the change. We call these situations "two-picture" problems because the primitive analysis leads us to sketches representing two (or more) system states. 

When streams are flowing through an open system, a primitive analysis leads us to represent the situation by a single sketch, perhaps like that in Figure 1.6. We call this a "one-picture" problem. In these situations we can extend the primitive analysis to include equations that represent inventories on selected quantities. We develop those equations here. 

Percentage of meteorites seen to fall. Chondrites. Over 90% of meteorites that are observed to fall out of the sky are classified as chondrites, samples that are distinguished from terrestrial rocks in many ways (3). One of the most fundamental is age. Like most meteorites, chondrites have formation ages close to 4.55 Gyr. Elemental composition is also a property that distinguishes chondrites from all other terrestrial and extraterrestrial samples. Chondrites basically have undifferentiated elemental compositions for most nonvolatile elements and match solar abundances except for moderately volatile elements. The most compositionaHy primitive chondrites are members of the type 1 carbonaceous (Cl) class. The analyses of the small number of existing samples of this rare class most closely match estimates of solar compositions (5) and in fact are primary source solar or cosmic abundances data for the elements that cannot be accurately determined by analysis of lines in the solar spectmm (Table 2). Table 2. Solar System Abundances of the Elements ... 

A possible reason that the problem of C < 0 did not receive much attention was the assertion [15] (BLH) that such an anomaly was forbidden. The proof was based on the statistical mechanical analysis of the primitive model of electrolytes between two oppositely charged planes, cr and —a. It was noticed in Ref. 10 that the BLH analysis missed a very simple contribution to the Hamiltonian, direct interaction between the charged walls, ItzLct (L is the distance between the walls). With proper choice of the Hamiltonian the condition on the capacitance would be C > 27re/L. It simply means that due to ionic shielding of the electric field, the capacitance exceeded its geometrical value corresponding to the electrolyte-free dielectric gap. 

The interpretation of phenomenological electron-transfer kinetics in terms of fundamental models based on transition state theory [1,3-6,10] has been hindered by our primitive understanding of the interfacial structure and potential distribution across ITIES. The structure of ITIES was initially studied by electrochemical and thermodynamic analyses, and more recently by computer simulations and interfacial spectroscopy. Classical electrochemical analysis based on differential capacitance and surface tension measurements has been extensively discussed in the literature [11-18]. The picture that emerged from... 

This instrumentation has exquisite sensitivity, which allows the analysis of single cancer cells (Hu et al., 2004). Our earlier work employed slow separation conditions and a rather primitive photodetection system. Our current system takes roughly 1 h to complete the two-dimensional capillary electrophoresis separation and employs state-of-the-art photodetectors. 

The analysis of the laboratory ice experiments reveals a diverse array of bio-logical-looking molecules with the potential to seed life. Cometary collisions with planets could deliver these molecules to a primitive Earth or indeed to all planets within the solar system. The frequency of the collisions depends somewhat on the local star and the structure of the solar system forming around it. 

As follows from the previous analysis for quasi and ordinary particles gases there exists a critical value of parameters a and b for which the least value of the distribution function for observable frequencies is observed. From the physical point of view this is in agreement with the absolute minimal realization of the most probable state. As in any equilibrium distribution, there is an unique most probable state which the system tends to achieve. In consequence we conclude that the observable temperature of the relic radiation corresponds to this state. Or, what is the same, the temperature of such radiation correspond to the temperature originated in the primary microwave cosmic background and the primitive quantum magnetic flow. 

Busfield A, Gilmour JD, Whitby JA, Turner G (2004) Iodine-xenon analysis of ordinary chondrite halide implications for early solar system water. Geochim Cosmochim Acta 68 195-202 Busso M, Gallino R, Wasserburg GJ (1999) Nucleosynthesis in asymptotic giant branch stars relevance for galactic enrichment and solar system formation. Annu Rev Astronom Astrophys 37 239-309 Cameron AGW (1969) Physical conditions in the primitive solar nebula. In Meteorite Research. Millman PM (ed) Reidel, Dordrecht, p 7-12... 

The analysis of fractionation law exponents quantifies the impression from the A -5 plots that aqueous Mg is related to primitive mantle and average crustal Mg by kinetic processes while carbonates precipitated from waters approach isotopic equilibrium with aqueous Mg. In any case, the positive A Mg values of carbonates relative to the primitive chondrite/mantle reservoir and crust is a robust feature of the data and requires a component of kinetic Mg isotope fractionation prior to carbonate formation, as illustrated schematically in Figure 3. 

Laser ablation combined with LA-MC-ICPMS provides a new dimension to the analysis of Mg isotopes in calcium aluminum-rich inclusions from primitive meteorites. Dispersion in 26Mg - Al/ Mg evolution lines can be correlated with mass-dependent variahons in 5 Mg that distinguish open-system from closed-system processes. The ultimate product of such studies will be a better understanding of the chronological significance of variations in Mg in these objects. 

The story became more complicated when in 1809 the Enghsh scientist William Hyde Wollaston (1766—1828) analyzed the sample mineral and declared that columbium was really the same element as tantalum ( Ta). This error is understandable given that the level of analytical equipment available to scientists in those days was fairly primitive. Also, tantalum and niobium are very similar metals that are usually found together and thus are difficult to separate for analysis. 

The D/H ratio of the sun is essentially zero all the primordial deuterium originally present has been converted into He dnring thermonuclear reactions. Analysis of primitive meteorites is the next best approach of estimating the hydrogen isotope composition of the solar system. 

Since boron concentrations in mantle minerals are exceedingly low, boron isotope analysis of mantle minerals are very restricted. On the basis of a boron budget between mantle and crust, Chaussidon and Marty (1995) conclnded that the primitive mantle had a 5 B-value of-10 2%c.ForMORB Spivack and Edmond (1987) and Chaussidon and Marty (1995) reported a 5 B-value of aronnd -4%c. Higher and lower 5 B-values observed in some ocean island basalts shonld be due to crustal assimilation (Tanaka and Nakamura 2005). 

Grady MM, PiUinger CT (1990) ALH 85085 nitrogen isotope analysis of a highly unusual primitive chondrite. Earth Planet Sci Lett 97 29 0... 

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