SUPPORTING INFORMATION

Sensitivity analysis of the proposed model.

The effect of the value of k2 on the predicted normalized total RSH concentration is presented
in Figure S1, where the fitting of the proposed model to the experimental results is also
shown. Curve 1 represents a typical stripping operation with high reaction rate constant of
reverse reaction so that reversible reaction does not lower the process. Accordingly, due to
stripping effects, Ctot/Co decreases as time proceeds; however the magnitude of reduction
differs greatly. Parameter k2, which represents the non-equilibrium effects, determines the
stripping rate significantly at high pH values and bends the curve of normalized
concentration. The bending is sudden at high flow rates of inert gas and smoother at low flow
rates. A decrease on k2 can cause an emission rate several magnitudes lower.

1,00
5
0,90
normalized concentration, Ctot/Co

0,80 4
0,70
0,60 3

0,50
2
0,40
0,30
0,20 1

0,10
Time, s
0,00
0 5000 10000 15000 20000 25000
1: k2=0.001 2:k2=0.0001
3:k2=0.00001 4:k2=0.000005
5:k2=0.000001 experimental data

Figure S1. Normalized concentration vs. time plot under different k2 parameter values: gas
flow rate Q=402 mL/min, pH=11.7, liquid volume VL=1.2 L

An increase of 100% in estimated k2 value can introduce an error of 8% for 5h stripping,

whereas a decrease of 80% results in an error of 9% for the same operation time. Below a
critical value of k2 (so that net reaction rate governs the mass transfer operation) two
characteristic phases of operation can be observed (curves 3-5); a first phase where a sharp
decrease in normalized total thiol concentration is observed while the initial available neutral
thiol is being stripped out and a second phase where the reversible reaction becomes the
limiting step, being the only source for strippable thiol.

In order to investigate the response of the proposed mass balance – based model to changes in
k2 and γ∞, simulated changes (duration time: 1h) in thiol (RSH/RS-) quantity and molar flow
rate of thiol leaving the liquid, are presented in Figures S2 and S3.
 5,0E-06 3,5E-03 3,0E-09
4,5E-06
3,0E-03
4,0E-06 2,5E-09
3,5E-06 2,5E-03
2,0E-09

FRSH, mol/s
NRS,mol
N RSH, mol

3,0E-06 2,0E-03
2,5E-06 1,5E-09
2,0E-06 1,5E-03
1,0E-09
1,5E-06 1,0E-03
1,0E-06 NRSH 5,0E-10
5,0E-04
5,0E-07 NRS 0,0E+00
0,0E+00 0,0E+00
0,0 1,0 2,0 3,0
0,2 0,5 1,0 1,5 2,0
k2/k2opt k2/k2opt

0,0E+00 5,0E-07 1,6E-09

0,9 1,0 1,1 1,2
0,0E+00 1,4E-09
-5,0E-07
1,2E-09
-5,0E-07
NRSH-N RSHopt, mol

1,0E-09

FRSH , mol/s
N RS-N RSopt,mol
-1,0E-06
NRSH -1,0E-06
8,0E-10
NRS
-1,5E-06
-1,5E-06 6,0E-10

-2,0E-06 4,0E-10
-2,0E-06
-2,5E-06 2,0E-10

0,0E+00
-2,5E-06 -3,0E-06
0,8 0,9 1,0 1,1 1,2
γ∞/γ∞opt
γ∞/γ∞opt

Figure S2. Simulated changes in thiol (RSH/RS-) quantity and molar flow rate of thiol
resulting from change in k2 and γ∞. Experimental conditions: pH=11.7, Q=402 mL/min,
VL=1.2 L, CRSHo=2.78 mM, T=301 Κ.
 9,0E-05 6,0E-06
8,0E-05 6,0E-08
7,0E-05 6,0E-06
6,0E-05 5,0E-08
N RSH, mol

5,9E-06

NRS,mol
5,0E-05 4,0E-08

FRSH, mol/s
4,0E-05
NRSH 5,9E-06
3,0E-05 3,0E-08
NRS
2,0E-05 5,8E-06 2,0E-08
1,0E-05
0,0E+00 5,8E-06 1,0E-08
0,2 0,5 1,0 1,5 2,0
0,0E+00
k2/k2/opt
0,0 0,5 1,0 1,5 2,0 2,5
k2/k2opt

0,00E+00 0,00E+00 6,00E-08

-1,00E-05 0,85 0,90 0,95 1,00 1,05 1,10 1,15 5,00E-08
-5,00E-09
-2,00E-05
NRSH-NRSHopt, mol

4,00E-08

FRSH, mol/s
NRS-NRSopt,mol
-3,00E-05 -1,00E-08
-4,00E-05 NRSH-NRSHopt 3,00E-08
NRS-NRSopt -1,50E-08
-5,00E-05
2,00E-08
-6,00E-05 -2,00E-08
-7,00E-05 1,00E-08
-2,50E-08
-8,00E-05 0,00E+00
-9,00E-05 -3,00E-08 0,80 0,90 1,00 1,10 1,20
γ∞/γ∞opt γ∞/γ∞opt

Figure S3. Simulated changes in thiol (RSH/RS-) quantity and the molar flow rate of thiol
resulting from change in k2 and γ∞. Experimental conditions: pH=8.5, Q=200 mL/min,
VL=1.0 L, CRSHo= 0.93 mM, T=301 Κ.

At pH=11.7 (Figure S2) there is a critical value near to the optimum, beyond which there is a
decrease in predicted quantity of ionic thiol due to high transformation rate of ionic to neutral
form of target compound. On the contrary, neutral thiol exhibits a linear increase vs.
parameter multiplier and the same behavior shows the molar flowrate of thiol stripped-out. At
pH=8.5 (Figure S3) neutral thiol and emission rate are insensitive to changes in k2 parameter
within the examined values of k2/k2opt.
Different behavior is predicted for the simulated change in neutral/ionic thiol quantity and the
emission rate resulting from change in limiting activity coefficient at infinite dilution (γ∞). A
Gaussian peak is observed which clearly demonstrates the extreme sensitivity of the model
simulations to uncertainty in value of γ∞. The contribution of γ∞ in the mass balance based
model is undoubtedly correlated with k2 parameter’s. Limiting activity coefficient controls
emission rate (FRSH) and through it the dynamic variations of RSH, RS- concentration profiles
whereas k2 parameter controls the neutral/ionic transformation and it is the crucial quantity
which governs the process at high pH values.

Uncertainty calculations
Sensitivity analysis.
Considering a conventional sensitivity analysis, the effect of changing individual model
parameters (E) on the estimation rate (F) is quantified using the following expression:
∂F E
SE = (S1)
∂E F
The variance of output ( σ pred 2 ) is the weighted sum of variance contributed by uncertainty in
the individual model parameters.

∑σ
6
σ pred 2 = Eη
2
= σ γ ∞ 2 S γ ∞ 2 + σ Po , RSH 2 S Po ,RSH 2 + σ Po , w 2 S Po , w 2 + σ N T 2 S N T 2 + σ PT 2 S PT 2 + σ FI 2 S FI 2 (S2)
η=1

The quantity S is given in the following table:

∞
Parameter γ Po,RSH Po,w NT PT FI
S (1-yw)/yI (1-yw)/yI yw/yI -(1-yw)/yI -1/yI 1

Table S1. Sensitivity factor calculated from equation (A1) for the model parameters

A lognormal distribution to describe uncertainty in input to the model is normal and

advantageous. The statistics (assumed and calculated) for the various contributions to
uncertainty is summarized in table S2 below:
Parameter Standard deviation (σ)
∞
γ 0.15 (1)
Po,RSH 0.20 (2)
Po,w 0.20 (2)
Ntot 0.006 (3)
Ptot 0.01 (2)
FI 0.01 (3)
measurement uncertainty 0.03 (4)

Table S2. Prediction uncertainty and the measurement uncertainty in terms of standard
deviation.
(1)
Uncertainty calculation based on experimental results obtained according the method
proposed by Richon D. et al.8 (1980) and Duhem and Vidal 9 (1978).
(2)
Reference 22.
(3)
Calculation based on contribution of volumes and time measurement.
(4)
Calculation based on reference curve uncertainty, on variance of 239nm and 412nm
wavelength, and on the repeatability of analytical methodology.

Uncertainty elements.24,25
There are general limitations to the mass balance approach. Inaccuracies in experiments and
analytical measurements of the present study and inaccuracies in numerical simulations can
lead to inaccuracies in estimates of thiol emissions.
Assuming that the experimental observations of neutral thiol concentration are independent of
the estimates for the model parameters (γ∞, Po,RSH, Po,w, Ntot, Ptot, FI), the total variance is given
by:
σ total 2 = σ meas 2 + σ pred 2
where σmeas is the variance of the analytical measurements and σpred the variance of the
predictive model.
Using the resulting standard deviations from sensitivity analysis and standard deviation for
the measurement error and assuming that both prediction and measurement uncertainties are
normally distributed, the 95% confidence bars which occur at ±1.96σtotal can be evaluated.
The measured and predicted thiol emission rate (FRSH) including parameter uncertainty and
measurement error are shown in Figure S4.

1,2E-08
8,0E-07
1,0E-08
7,0E-07
Emission rate, mol/s

8,0E-09 6,0E-07

Emission rate, mol/s

5,0E-07
6,0E-09
4,0E-07

4,0E-09 3,0E-07

2,0E-07
2,0E-09
1,0E-07

0,0E+00 0,0E+00
0 5000 10000 15000 20000 25000 0 2000 4000 6000 8000
(I) Time, s (II)
Time, s

Figure S4. Simulated predicted response represented by the solid line and error bars,
measured response represented by the solid points. (I) Q=402 mL/min, pH=11.7, VL=1.2 L,
CRSHo=2.78 mM, 301 K, (II) Q=200 mL/min, pH=8.5, VL=1.0 L, CRSHo= 0.93 mM, T=301 Κ.

Predicted errors are large during the very early moments of process especially at pH=11.7.
During this period field conditions are not totally reproducible which will result in errors in
predictive simulations (“worst-case” simulation).