Abstract
An explicit set of general methods for the experimental determination of the rates k1 and k2 of consecutive pseudo-first-order reactions is described and discussed. These rely on the direct simultaneous analytical quantitation of the starting material, intermediate, and product of the reaction, and thus differ from present techniques based on measurement of coreactant consumption or coproduct appearance. The quantity kenv = k1k2/(k1 + k2) is shown to define a good “envelope” approximation to product formation according to the simple law 100% [1 − exp(−kenvt)]. The theory of envelopes is useful for comparing overall rates of reactions with widely differing values of κ = k2/k1. The kinetic pattern of thiolysis of dithiasuccinoyl amino acids to carbamoyl disulfide intermediates to product free amino acids is analyzed and shown to agree quantitatively with theory.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 114-122 |
| Number of pages | 9 |
| Journal | Analytical Biochemistry |
| Volume | 109 |
| Issue number | 1 |
| DOIs | |
| State | Published - Jan 1 1980 |
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The explicit analysis of consecutive pseudo-first-order reactions : Application to kinetics of thiolysis of dithiasuccinoyl (Dts) amino acids. / Barany, George.
In: Analytical Biochemistry, Vol. 109, No. 1, 01.01.1980, p. 114-122.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - The explicit analysis of consecutive pseudo-first-order reactions
T2 - Application to kinetics of thiolysis of dithiasuccinoyl (Dts) amino acids
AU - Barany, George
PY - 1980/1/1
Y1 - 1980/1/1
N2 - An explicit set of general methods for the experimental determination of the rates k1 and k2 of consecutive pseudo-first-order reactions is described and discussed. These rely on the direct simultaneous analytical quantitation of the starting material, intermediate, and product of the reaction, and thus differ from present techniques based on measurement of coreactant consumption or coproduct appearance. The quantity kenv = k1k2/(k1 + k2) is shown to define a good “envelope” approximation to product formation according to the simple law 100% [1 − exp(−kenvt)]. The theory of envelopes is useful for comparing overall rates of reactions with widely differing values of κ = k2/k1. The kinetic pattern of thiolysis of dithiasuccinoyl amino acids to carbamoyl disulfide intermediates to product free amino acids is analyzed and shown to agree quantitatively with theory.
AB - An explicit set of general methods for the experimental determination of the rates k1 and k2 of consecutive pseudo-first-order reactions is described and discussed. These rely on the direct simultaneous analytical quantitation of the starting material, intermediate, and product of the reaction, and thus differ from present techniques based on measurement of coreactant consumption or coproduct appearance. The quantity kenv = k1k2/(k1 + k2) is shown to define a good “envelope” approximation to product formation according to the simple law 100% [1 − exp(−kenvt)]. The theory of envelopes is useful for comparing overall rates of reactions with widely differing values of κ = k2/k1. The kinetic pattern of thiolysis of dithiasuccinoyl amino acids to carbamoyl disulfide intermediates to product free amino acids is analyzed and shown to agree quantitatively with theory.
UR - http://www.scopus.com/inward/record.url?scp=0019326359&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0019326359&partnerID=8YFLogxK
U2 - 10.1016/0003-2697(80)90018-4
DO - 10.1016/0003-2697(80)90018-4
M3 - Article
C2 - 7469008
AN - SCOPUS:0019326359
VL - 109
SP - 114
EP - 122
JO - Analytical Biochemistry
JF - Analytical Biochemistry
SN - 0003-2697
IS - 1
ER -