Nature exhibits a curious asymmetry between the left and the right, which is generally called ‘chira — Physical Chemistry — Kinetics Chemistry Question
Asymmetric autocatalysis – the numerical experiment
Nature exhibits a curious asymmetry between the left and the right, which is generally called ‘chiral asymmetry’. Indeed, living organisms contain mostly L-amino acids and D-carbohydrates. One of the possible explanations of this phenomenon is based on the idea of autocatalysis. Chiral (asymmetric) autocatalysis is a reaction in which every chiral product serves as the catalyst of its own formation. In such reactions small initial excess of one of the enantiomers can increase exponentially in time.
Consider the kinetic scheme explaining this phenomenon. Two Enantiomers, XL and XD, are reversibly formed from achiral reagents T and S:
S + T <=> XL (1) (with rate constants k1, k_-1)
S + T <=> XD (2) (with rate constants k1, k_-1)
S + T + XL <=> 2 XL (3) (with rate constants k2, k_-2)
S + T + XD <=> 2 XD (4) (with rate constants k2, k_-2)
XL + XD → P (5) (with rate constant k3)
Enantiomers react with each other giving the product P. The reactions take place in an open system, where constant concentrations of reagents S and T are maintained.
The system of rate equations can be solved numerically using any of the mathematical packages, for example Mathematica, MathCad, etc. Alternatively, you may use the program KINET posted on the official website www.icho39.chem.msu.ru. Let us assume the following values of rate constants (in arbitrary units): k1 = 0.5, k–1 = 0.1, k2 = 0.5, k–2 = 0.2, k3 = 0.5.
Procedure
For numerical solution of the systems of differential equations mathematical packages use different commands. In Mathematica it is done by the function NDSolve. The arguments are the list of equations, initial conditions and a time interval. For example, the system of equations:
a'(t) = -a(t)p(t)
p'(t) = a(t)p(t) - 2p(t)
with the initial conditions a(0) = 2, p(0) = 0.5 in a time interval from t = 0 to t = 10 is solved numerically by the command:
sol=NDSolve [{a ' ==-a *p , p ' == a *p -2*p , a == 2, p == 0.5}, {a, p}, {t, 0,10}]
The obtained solution is presented on the graph by the command Plot:
Plot [Evaluate [{a , p }/.sol, {t, 0,10}], PlotRange-> All]
Compare equations 1 and 2 or 3 and 4 in the Scheme above. Why are the rate constants identical for enantiomers XL and XD?
The control parameter for this problem is the product of concentrations of reagents. Solve the system of kinetic equations numerically and draw on one graph the kinetic curves for XL and XD using the initial conditions: [XL]0 = 0, [XD]0 = 0.01. Consider two opposite cases: [S] [T] is small, [S] [T] is large. By varying the parameter [S] [T] determine its “break” value at which the shape of kinetic curve(s) changes drastically.
At fixed value [S] [T] = 5 study the influence of initial chiral asymmetry on kinetic curves. Consider two cases: [XD]0 = 0.001, [XD]0 = 0.1.
Let us determine which elementary reactions are essential for chiral asymmetry amplification.
Model Answer
The more the initial chiral asymmetry the earlier kinetic curves separate from each other.
Consider the role of reversibility. For this purpose, given the same initial concentrations compare kinetic curves for two mechanisms: with reversible (k–1 ≠ 0; k–2 ≠ 0) and with irreversible formation of the enantiomers (k–1 = k–2 = 0).
Model Answer
Reversible stages are not necessary for amplification of chiral asymmetry.
Consider the simplified scheme in which the first two reactions are absent. Whether an amplification of chiral asymmetry is possible in such system?
Model Answer
These reactions are not necessary for amplification of chiral asymmetry.
Compare the open and closed systems. You have already treated the open system. In the closed system the reagents S and T are no more introduced to a reaction vessel during reaction, therefore they should be included in the system of kinetic equations. Whether or not amplification of chiral asymmetry is possible in a closed system?
Draw the conclusions. What conditions are necessary for amplification of chiral asymmetry to be observed? What elementary stages appear to be essential for it?
Model Answer
In a closed system amplification of chiral asymmetry is not possible. In an open system the essential stages are (3) – (5).