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6.

Evaluation of intermediate and mechanism

The reduction reaction of nitrate could decompose to intermediate as nitrite and

products which are NH4+ and N2. Considering the classification of toxic, NH4+ is toxicity as

undesired substance. Fig. XX shows the concentration profiles of each catalyst, PdCu-Fe(0),

CuPd-Fe(0) and NZVI through the reaction period. As can be seen in all chemicals, the

nitrate removal was not significant difference at concentration approximately 15 mg/L of N.

While the amount of NH4+ was produced the highest product comparing N2 on NZVI

followed by PdCu-Fe(0) and CuPd-Fe(0) with 13.36, 11.21 and 10.78 mg/L of N,

respectively. Considering at N2, The highest selectivity of N2 was found on PdCu-Fe(0) with

6.58 mg/L of N subsequent to CuPd-Fe(0) and NZVI with 5.47 and 2.31 mg/L of N,

respectively. As reaction results, kinetics of nitrate removal could be presumed as depicted in

Fig. XX. There are two types of pathway reaction classified from reaction mechanism (XXX

ref. อาจจะขยายว่าทาไม Fe(0) เป๋ นแบบนึง). All reactions were supposed as elementary reaction

written in Eq. (1 ̶ 4) for pathway (a), Eq. (5-8) for pathway (b).

dC NO 
3
 k1C NO  (1)
dt 3

dC NO 
2
 k1C NO   (k 2 C NH   k 3 C N 2 ) (2)
dt 3 4

dCNH 
4
 k 2 C NO  (3)
dt 2

dC N 2
 k 3 C NO  (4)
dt 2

dC NO 
3
 (k1  k 2  k 3 )C NO  (5)
dt 3

dC NO 
2
 k1C NO  (6)
dt 3
dCNH 
4
 k 2 C NO  (7)
dt 3

dC N 2
 k 3 C NO  (8)
dt 3

(a)
30
Concentration of N (mg/L)

25

20

15

10

0
0 10 20 30 40 50 60
time (min)

(b)
30
Concentration of N (mg/L)

25

20

15

10

0
0 10 20 30 40 50 60
time (min)
(c)
30

Concentration of N (mg/L) 25

20

15

10

0
0 10 20 30 40 50 60
time (min)

Figure XX. Profiles of nitrate and its intermediates in the nitrate removal over (a) PdCu-

Fe(0), (b) CuPd-Fe(0) and NZVI with conditions; 100 mg/L, 30 °C, pH 7

(a)

N H 4+
k2

k1
N O 3- N O 2-
k3

N2

(b)
N O 2-
k1

k2
N O 3- N H 4+

k3

N2

Figure XX. Scheme of proposed reaction pathway of nitrate removal (a) on PdCu-

Fe(0) and CuPd-Fe(0) (b) on NZVI

Obtained kinetic rate constants for each elementary reaction of nitrate removal on

PdCu-Fe(0), CuPd-Fe(0) and NZVI are summarized in Table XX. In the case of PdCu-Fe(0)

and CuPd-Fe(0) as scheme reaction (a), the rate constant of nitrate decomposition ( k1 ) were

2.92 and 2.85, respectively. The relative transformation of NO2- to NH4+ ( k 2 ) were 33.35 on

PdCu-Fe(0) and 17.45 on CuPd-Fe(0). The rate constant of the transformation of NO2- to N2

as desired product ( k 3 ) on PdCu-Fe(0) reveals obviously higher than on CuPd-Fe(0) which

were 20.30 and 8.81, consecutively. Regarding NZVI as scheme of proposed pathway (b), the

rate constant of nitrate removal reveals lower than both former catalysts. The relative rate

constant k2 and k3 were 20.50 and 3.55, respectively. This result confirmed that NZVI

showed ineffective on N2 selectivity. Relative to overall results, the kinetic rate constants of

kinetic study described that the removal of nitrate can effectively transform to N2 selectivity

on PdCu-Fe(0).

Table XX Kinetic constants of intermediate products of nitrate removal on PdCu-Fe(0),

CuPd-Fe(0) and NZVI

rate constant
PdCu-Fe(0) CuPd-Fe(0) NZVI
(102 min-1)
k1 2.92 2.85 2.73
k2 33.35 17.45 20.50
k3 20.30 8.81 3.55