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Water and Solute Permeability of Plant Cuticles: Measurement and ...

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6.3 Diffusion with Changing Donor Concentrations: The Transient State 183<br />

Table 6.7 Comparison <strong>of</strong> partition coefficients <strong>and</strong> permeances determined at 25 ◦ C in the steady<br />

state <strong>and</strong> with UDOS<br />

CM Steady state UDOS<br />

K cuticle/buffer P(m s −1 ) P ∗ (m s −1 ) K soco/buffer P ∗ (m s −1 )<br />

P ∗ UDOS<br />

P ∗ steady state<br />

1 416 1.05 × 10 −8 2.52 × 10 −11 400 1.75 × 10 −11 0.69<br />

2 396 1.49 × 10 −8 3.76 × 10 −11 386 3.02 × 10 −11 0.86<br />

3 326 4.76 × 10 −8 14.60 × 10 −11 325 12.60 × 10 −11 0.86<br />

4 398 11.20 × 10 −8 28.10 × 10 −11 389 24.50 × 10 −11 0.87<br />

Taken from Bauer <strong>and</strong> Schönherr (1992). Donor solutions had a pH <strong>of</strong> 3.0<br />

calculated from the mass <strong>of</strong> the CM, the volume <strong>of</strong> the donor solution, the decrease<br />

in donor concentration, <strong>and</strong> the equilibrium concentration <strong>of</strong> the donor. The donor<br />

solution was removed, <strong>and</strong> borax buffer was added as receiver <strong>and</strong> k ∗ was measured<br />

in an UDOS experiment. P ∗ was calculated from (6.16) using the weight average<br />

thickness (ℓCM) <strong>of</strong> the CM, rather than the unknown thickness <strong>of</strong> the sorption<br />

compartment (ℓsoco).<br />

Partition coefficients were virtually identical in the two types <strong>of</strong> experiments<br />

(Table 6.7), except that K soco/buffer tended to be slightly lower, possibly because the<br />

limiting skin was not yet in equilibrium after 3 h <strong>of</strong> loading. Steady state permeance<br />

(P) varied among CM by a factor <strong>of</strong> about 10, which is typical for CM <strong>of</strong><br />

most species. P ∗ values calculated for steady state experiments varied by the same<br />

factor because K cuticle/buffer varied between CM only slightly. Agreement between<br />

P ∗ obtained from rate constants determined in UDOS experiments (6.16) <strong>and</strong> those<br />

calculated from steady state data (6.17) is very good, considering that both permeances<br />

varied among CM by a factor <strong>of</strong> more than 10. This shows that both types <strong>of</strong><br />

experiment provide comparable data, <strong>and</strong> P can be calculated from rate constants<br />

(k ∗ ) measured using UDOS.<br />

P ∗ calculated as ℓCM × k ∗ (UDOS) is consistently smaller than P ∗ calculated<br />

from steady state data (Table 6.7). The factor averaged over all four CM is 0.805,<br />

<strong>and</strong> this cannot be attributed to differences in partition coefficients, which amount<br />

for only 2% on average. The limiting skin has an unknown but finite thickness,<br />

hence ℓsoco × k ∗ should be smaller than ℓCM × k ∗ . However, P ∗ calculated from<br />

rate constants were smaller than P ∗ calculated from steady state permeance P <strong>and</strong><br />

partition coefficients. It appears that ℓCM systematically underestimates the real path<br />

length.<br />

6.3.2.1 Estimating <strong>Solute</strong> Mobility from Rate Constants<br />

Steady state permeance (P) is proportional to the partition coefficient (2.18). Permeance<br />

<strong>of</strong> CM is determined by the thickness <strong>of</strong> the limiting skin, while K reflects<br />

solubility in the sorption compartment. These definitions result in

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