Chemical Analysis. Francis Rouessac
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Название: Chemical Analysis

Автор: Francis Rouessac

Издательство: John Wiley & Sons Limited

Жанр: Химия

Серия:

isbn: 9781119701347

isbn:

СКАЧАТЬ (1.42) type.

Schematic illustration of analysis by internal normalization method.

      One of the compounds, 3 for example, is chosen as the substance for internal normalization. This compound 3 will serve to calculate the relative response factors K1/3 and K2/3 for compounds 1 and 2 with respect to 3 . As previously deduced:

upper K Subscript 1 slash 3 Baseline equals StartFraction upper K 1 Over upper K 3 EndFraction equals StartFraction m 1 dot upper A 3 Over m 3 dot upper A 1 EndFraction a n d upper K Subscript 2 slash 3 Baseline equals StartFraction upper K 2 Over upper K 3 EndFraction equals StartFraction m 2 dot upper A 3 Over m 3 dot upper A 2 EndFraction

      Given that mi = Ci.V, then the following equations for K1/3 and K2/3 are obtained:

upper K Subscript 1 slash 3 Baseline equals StartFraction upper C 1 dot upper A 3 Over upper C 3 dot upper A 1 EndFraction a n d normal upper K Subscript 2 slash 3 Baseline equals StartFraction upper C 2 dot upper A 3 Over upper C 3 dot upper A 2 EndFraction

      1.17.2 Chromatogram of the Sample – Calculation of the Concentrations

      The next step consists in injecting a specimen of the mixture to be measured containing compounds 1, 2, and 3 . Labelling the elution peaks asupper A prime Subscript 1 Baseline comma upper A prime Subscript 2 Baseline comma and upper A prime Subscript 3 will give direct access to the percentage mass composition of the mixture represented by x1, x2, and x3 via three equations of the following form:

x Subscript i Baseline percent-sign equals StartFraction upper K Subscript i slash 3 Baseline dot upper A prime Subscript i Baseline Over upper K Subscript 1 slash 3 Baseline dot upper A prime Subscript 1 Baseline plus upper K Subscript 2 slash 3 Baseline dot upper A prime Subscript 2 Baseline plus upper A prime Subscript 3 Baseline EndFraction times 100 w i t h i equals 1 o r 2 o r 3 period

      The condition of normalization is that x1 + x2 + x3 = 100

      If the procedure is extrapolated to n components normalized to compound j (internal reference), a general expression for the response factor of a given compound i can be obtained:

      (1.46)upper K Subscript i slash j Baseline equals StartFraction upper C Subscript i Baseline dot upper A Subscript j Baseline Over upper C Subscript j Baseline dot upper A Subscript i Baseline EndFraction

      It is also possible to determine Ki/j by plotting a concentration–response curve for each of the solutes.

      In a mixture containing n solutes, if upper A prime Subscript normal i designates the area of the elution peak of compound i, and if the internal reference is j, then the content of compound i will obey the following equation:

      (1.47)x Subscript i Baseline percent-sign equals StartFraction upper K Subscript i slash j Baseline dot upper A prime Subscript i Baseline Over sigma-summation Underscript i equals 1 Overscript n Endscripts upper K Subscript i slash j Baseline dot upper A prime Subscript 1 Baseline EndFraction times 100

      This method is ideal to monitor rates of advancement of a chemical reaction and, at the same time, to follow the conversion kinetics.

      1 Chromatography is a separation method and also an analytical method. It is a very reliable method, with continued innovation in order to separate, purify, identify, and quantify chemical species.

      2 It is based on the adsorption or partition, depending on various parameters and interactions, of chemical species between two immiscible phases, one fixed or stationary (SP) and the other mobile (MP).

      3 There are many chromatographic techniques that differ in the process used, the nature of phases, physico‐chemical equilibria, the physical state, etc., and just as many classifications are possible depending on the criterion retained!

      4 To each compound, we assign a distribution factor K = CS /CM as a function of its concentration in the two phases. For each type of chromatography, thermodynamic relationships apply. From K (which is not a constant), we can calculate ΔH, ΔS, and ΔG for the separation in question.

      5 A document inseparable from any chromatographic analysis, the chromatogram, or elution curve, represents the graphic recording of concentration over time. It provides information on the analysed sample and on the quality of the separation in progress.

      6 One peak = one compound is the ideal situation. At column outlet, we treat the ideal peak as a Gaussian peak (hence the parameters σ, δ, ω), but the reality may be different. An ideal chromatogram has peaks that do not overlap and which are at least somewhat spaced out. A peak alone does not enable the absolute identification of a compound.

      7 A number of parameters can be used to better characterize each separation: efficiency, retention, separation, and resolution. The flow rate of the mobile phase has an influence on efficiency. Many empirical equations, not reported in this chapter, are offered to mathematically define the behaviour of analytes during elutions with a gradient.

      8 The speed of progression of the mobile phase with respect to the stationary phase has an essential influence on separation quality. A hyperbolic function, formed from the addition of three independent terms, known as the Van Deemter equation, demonstrates the existence of an optimal linear speed, i.e. leading to a minimum value of HETP.

      9 First established for GC, and later adapted to HPLC, the three terms of the previous equation refer to preferential paths (turbulent diffusion), to longitudinal diffusion, and to resistance to mass transfer.

      10 The quantification of analytes using chromatography is founded on the relationship between the mass and the area of the corresponding peak on the chromatogram. There are three methods, called the external standard method, internal standard method, and internal normalization method. The first is by far the most used because it is the quickest when it comes to processing a large number of analyses. Chromatograms equipped with a sample holder carousel and an automatic injection device make this method very reliable.

      1 For a given solute, show that the analysis time (which we can assume is equal to the retention time of the most retained compound) depends, amongst other things, on the column length СКАЧАТЬ