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journal of hydrogen energy 38 (2013) 14391 e 14401 Available online at www.sciencedirect.com journal

Available online at www.sciencedirect.com

Available online at www.sciencedirect.com journal homepage: www.elsevier.com/locate/he

journal homepage: www.elsevier.com/locate/he

journal homepage: www.elsevier.com/locate/he Electrochemical investigation of the Bunsen reaction in the
journal homepage: www.elsevier.com/locate/he Electrochemical investigation of the Bunsen reaction in the

Electrochemical investigation of the Bunsen reaction in the sulfur eiodine cycle

of the Bunsen reaction in the sulfur e iodine cycle Zhi Ying, Yanwei Zhang * ,

Zhi Ying, Yanwei Zhang * , Qiaoqiao Zhu, Pingan Peng, Zhihua Wang, Junhu Zhou, Jianzhong Liu, Kefa Cen

State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

article info

 

abstract

Article history:

 

The Bunsen reaction, as a part of the sulfur e iodine thermochemical cycle, was studied

Received 1 July 2013

 

using an electrochemical cell. The effects of current density, operating temperature, H 2 SO 4

Received in revised form

 

concentration in the anolyte, HI concentration and I 2 /HI molar ratio in the catholyte were

29 August 2013

 

explored. Both the H 2 SO 4 in anolyte and the HI in catholyte were concentrated during

Accepted 5 September 2013

 

electrolysis. Increasing current density amplified this H 2 SO 4 and HI concentration, while

Available online 2 October 2013

the other operating parameters also varied the anolyte and catholyte concentration. The

 

transport properties of the cation exchange membrane were examined. The electrode

 

Keywords:

 

current efficiency remained close to 100% for most runs except those at high current

Sulfur e iodine cycle

 

density. Both the average cell voltage and the heat equivalent of electric energy were

Electrochemical Bunsen reaction

 

determined at different conditions.

Electrolysis

 

Crown Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All

Cation exchange membrane

 

rights reserved.

Hydrogen production

 

1.

Introduction

 

(as a HI solution). Both acids are purified, concentrated, and then decomposed into hydrogen and oxygen, as shown in Reactions (2) and (3). The traditional direct contact mode of the Bunsen reaction requires a large excess of both iodine and water with respect to their stoichiometric values [1]. The excess iodine induces a separation of the solution produced into two immiscible phases [2,3] and the excess of water makes the reaction thermodynamically more favorable [4]. One of the disadvantages of the traditional SI cycle is that a large amount of energy is required to remove the excess iodine and water before the decomposition of HI [5]; moreover the circulation of iodine in the whole cycle is undesirable, due to its corrosive characteristics. Therefore, the overall thermal efficiency of the SI cycle is greatly reduced. In recent years, some alternative ways for carrying out the Bunsen reaction have been proposed in order to reduce the

The sulfureiodine (SI) thermochemical cycle, first proposed by General Atomics [1], is considered as one of the most prom- ising routes for massive hydrogen production. The SI process consists of the Bunsen Reaction (1) and the hydriodic acid and sulfuric acid decomposition Reactions (2, 3) , listed as follows:

 

293 K

393 K H 2 SO 4 þ 2HI

 

SO 2 þ I 2 þ 2H 2 O

!

(1)

2HI

573 K

! 773 K H 2 þ I 2

 

(2)

1073 K

1273

K SO 2 þ H 2 O þ 0: 5O 2

 

(3)

H 2 SO 4

!

Reaction (1), known as the Bunsen reaction, produces sul- furic acid (as an aqueous H 2 SO 4 solution) and hydriodic acid

* Corresponding author . Tel.: þ 86 571 87952040; fax: þ86 571 87951616. E-mail address: zhangyw@zju.edu.cn (Y. Zhang).

0360-3199/$ e see front matter Crown Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

excess amounts of iodine and water [6]. The addition of a precipitating agent, such as lead sulfate, was proposed to remove iodide and thus induce separation of the two acids without the excess of iodine [6]. Reaction solvents, such as liquid SO 2 , tributylphosphate (TBP), ionic liquids, and molec- ular solvents, were used to extract the HI produced in the Bunsen reaction [6e 9]; therefore, the presence of excess water can be avoided. Application of an electrochemical cell to the Bunsen reaction [10] is also a potential alternative. The elec- trolysis cell consists of two electrodes and two compartments separated by a cation exchange membrane. Gaseous SO 2 dis- solved in H 2 SO 4 solution and solid iodine dissolved in HI so- lution is used as anolyte and catholyte, respectively. The reactions at the anode and cathode are:

Anode :

SO 2 þ 2H 2 O /H 2 SO 4 þ 2H þ þ 2e

ðE 0; a ¼ þ0: 172 VÞ

 

(4)

Cathode :

I 2 þ 2H þ þ 2e /2HI

ðE 0; c ¼ þ0: 535 V Þ

(5)

This method offers several advantages: (1) the required amount of iodine and water is reduced and the liquideliquid separator can be dropped; (2) it increases the concentration of H 2 SO 4 and HI simultaneously; (3) the recirculation of unreac- ted reactant is reduced in the overall process. Disadvantage of this electrochemical method is that it requires electric power for electrolysis. The Bunsen reaction was studied by Nomura et al. in an electrochemical membrane reactor operated at room tem- perature [10]. Currentevoltage characteristics were evaluated and this study showed that the total resistance between the electrodes was independent of the H 2 SO 4 concentration and decreased with declining I 2 /HI molar ratio. The overpotential at the anode was reduced by addition of a small amount of HI to the anolyte. In another experiment [11] , conducted in a temperature range of 290 e333 K, the resistance between the electrodes decreased with rising operating temperature, but it increased with rising H 2 SO 4 concentration. Thermal efficiency diminished with rising current density and H 2 SO 4 concentra- tion. The same group [12] found that thermal efficiency grew with rising HI concentration and a maximum thermal effi- ciency of 38.9% was obtained. In recent years, a group at the Indian Institute of Tech- nology Delhi performed studies on the electrochemical Bun- sen reaction. Cross-contamination through the membrane was measured [13] and showed that the electroosmotic flow induced by the current enlarged the concentration of sulfate ions and SO 2 in the catholyte and reduced the concentration of iodide ions in the anolyte. The same group characterized platinum and graphite electrodes using linear sweep voltam- metry (LSV) and cyclic voltammetry (CV) [14]. Areal-resistance of the membrane was measured at different operating con- ditions [15]. Effects of anolyte pressure, catholyte pressure, temperature, H 2 SO 4 concentration in the anolyte, HI concen- tration and I 2 /HI molar ratio in the catholyte on cell voltage were investigated [16]. The concentration of HI and H 2 SO 4 is one of the important advantages for the electrochemical Bunsen reaction. More- over, it is desirable to study the variation of anolyte and catholyte concentration during electrolysis at different

operating conditions. The transport properties of the cation exchange membrane strongly affect the cell performance, yet concrete data has not been reported in literature. In this work, the effects of current density, temperature, initial H 2 SO 4 concentration in the anolyte, initial HI concentration and I 2 /HI molar ratio in the catholyte on the evolution of anolyte and catholyte concentration were studied. Cell voltage was recorded during electrolysis. The transport properties of the membrane were determined, and for different runs the cur- rent efficiency and energy consumption during electrolysis were also calculated.

2.

Experimental

2.1. Experimental setup

The Bunsen reaction was carried out in the experimental setup shown in Fig. 1. It mainly consists of an electrochemical cell, anolyte and catholyte reservoirs, the solution recircula- tion section between cell and reservoir, and a D.C. power supply. Fig. 2 shows a schematic diagram of the electro- chemical cell (Hephas Energy Co., Ltd.), consisting of two graphite electrodes and a Nafion 117 membrane (DuPont Co., USA); the effective membrane area was 12.25 cm 2 (3.5 cm 3.5 cm). Two rubber gaskets (170 mm thickness) were used at both sides of the membrane to prevent the intermix- ing of anolyte and catholyte. The temperature of the cell was controlled by means of a temperature controller (Hephas En- ergy Co., Ltd.). Two double-jacketed glass reservoirs operating at atmospheric pressure were placed on magnetic stirrers, and temperature was controlled using a thermostatic water bath (GX-2010, Shanghai Bilang Instrument Co.). Teflon tubes were employed to connect the reservoirs with each compartment of the cell. Two peristaltic pumps (BT100-2J, Baoding Longer Precision Pump Co., Ltd.) were used for circulating the solu- tions. In order to avoid heat dissipation, the teflon tubes were wrapped with heat insulation cotton. A D.C. power supply (PAN16-10A, KIKUSUI ELECTRONICS CORP., Japan) provided a constant current to the cell and monitored the cell voltage.

2.2. Electrolysis

Table 1 lists the operating conditions for the electrochemical Bunsen reaction. The total amount of water (the sum of water in the acids and the extra feed water) was fixed at 50 g for both anolyte and catholyte. The anolyte reservoir was initially filled with known amounts of sulfuric acid (about 98 wt. %, Quzhou Juhua reagent Co., Ltd.) and deionized water, while the cath- olyte reservoir was filled with known amounts of hydriodic acid (approximately 56 wt%, Shanghai Kefeng Industrial Co., Ltd.), iodine ( >99.9%, Chinasun Specialty Products Co., Ltd.) and deionized water. Both solutions were recirculated through their respective loops by two peristaltic pumps, the flow rate of both anolyte and catholyte was fixed at 10 ml/min. To start the test, the stirrer, the thermostatic water bath, and the temperature controller were switched on. After the sys- tem had reached the desired temperature, gaseous SO 2 was continuously fed at a constant flow rate of 20 ml/min into the H 2 SO 4 solution of the anolyte reservoir. This bubbling

D.C supply MFC Anode Cathode SO 2 H 2 SO 4 solution Magnetic stirrer Two
D.C supply
MFC
Anode
Cathode
SO 2
H 2 SO 4 solution
Magnetic stirrer
Two gaskets & a
cation exchange
membrane
HI-I 2 solution
Magnetic stirrer
Peristaltic pumps

Fig. 1 e Experimental setup used for the electrochemical Bunsen reaction.

procedure was conducted for 1 h before the start of electro- chemical reactions. Then, electrolysis was performed in the constant current mode supported by the D.C. power. The Bunsen reaction was carried out for 4 h, and the cell voltage was continuously recorded. Anolyte and catholyte were sampled periodically and analyzed by means of an autoti- trator (ZDJ-5, Shanghai Leici Instrument Co.). Solutions of 0.5 N NaOH, 0.05 N KIO 3 , and 0.1 N Na 2 S 2 O 3 were used to titrate H þ , I , and I 2 , respectively. To minimize the errors resulted from sampling and analysis, three samples were taken for measuring each ion; then, the average value and deviation of the H þ , I , and I 2 concentration were determined.

3. Results and discussion

3.1.

Theoretical

The theoretical moles of H 2 SO 4 and HI formed during elec- trolysis can be calculated using Faraday’s law [13,14]:

DN 0

i

¼

It

nF

ði ¼ H 2 SO 4 ; HIÞ

(6)

where I , t , and F are the constant current (A), the electrolytic time (s), and the Faraday constant (96,485 C/mol); n is the number of electrons required per mole of H 2 SO 4 or HI formed in the half cell reaction. In theory, SO 2 loses two electrons at the anode, consumes a water molecule, and produces SO 4 and H þ ions; thus the H 2 SO 4 concentration should steadily increase during electrolysis.Meanwhile, a portion of the H þ generated at the anode transports to the cathode through the membrane, and then constitutes HI with I ions reduced from I 2 ; therefore, the HI concentration should also rise, while the I 2 concentra- tion is lessening during electrolysis. However, in practice the H þ and I molality in the catholyte obtained through titration is not equal; this is due to the three following effects:

2

(1) The reduction rate of I 2 at the cathode is not equal to the transport rate through the Nafion 117 membrane, and once

the reduction rate of I 2 at cathode exceeds the transport rate of H þ through membrane, the I molality will become higher than the H þ molality, then HI concentration de- pends on the H þ concentration, otherwise, the molality of H þ is higher than that of I , and HI molality is determined by I molality. (2) The concentration of H þ in the anolyte is much higher than that of H þ in the catholyte. Hence, permeation of H þ from the anode to the cathode compartment may occur even without current passing. Even more H þ can migrate from the anode compartment to the cathode if current is applied. (3) Electroosmotic flow from anode to cathode occurs along with the migration of hydronium ions, leading to rising concentrations of SO 4 and SO 2 in the catholyte and diminution of I and I 2 in the anolyte [13] . As a result, the weight of catholyte may increase and side reactions may occur.

2

All effects above contribute to differences between the H þ and the I molality in the catholyte. The standard electrode potential (vs. standard hydrogen electrode (SHE)) of anode E 0, a is þ0.172 V, and that of cathode E 0, c is þ 0.535 V. Then the equilibrium voltage of the cell is 0.535 V 0.172 V ¼ 0.363 V if the cell works as a voltaic cell. However, in practice, electrode and electrolyte overpotentials require that some electric power must be supplied to the

system. The practical anode potential E a and cathode poten- tial E c are as follows (using Nernst equation) [17]:

E a ¼ E 0; a þ RT

2F

a 4

ln a SO

2

4

$

H

þ

p

SO

2

! ¼ 0 : 172 þ

$a 4

8: 31T 2 96485 ln a SO

2

4

H

þ

p

SO 2

!

(7)

E c ¼ E 0 ;c þ RT

2F

ln a I ! ¼ 0: 535 þ

2

a

2

I

!

a I

2

2

I

2 96485 ln a

8

: 31T

(8)

Here, a SO , a H þ are the activity of species and p SO 2 is the relative pressure SO 2 in the anolyte, dimensionless. a I 2 , a I are

2

4

journal of hydrogen energy 38 (2013) 14391 e 14401 Fig. 2 e Schematic diagram of the

Fig. 2 e Schematic diagram of the electrochemical cell. (i) cation exchange membrane, (ii) rubber gasket, (iii) graphite electrode, (iv) conductive plate, (v) aluminum plate, (vi) insulator, (vii) heater.

the activity of species in the catholyte, dimensionless. R, T, and F are gas constant (8.31 J mol 1 K 1 ), temperature (K), and Faraday constant (96,485 C/mol). Then, the anode/cathode overpotential ( h a /h c ) is:

!

(9)

h a ¼ E a E 0;a ¼ RT ln a SO

2

4

$

a 4

H

þ

2

F

p

SO

2

h c ¼ E c E 0; c ¼ RT 2F ln a I !

2

a

2

I

(10)

The overpotential relates to the charge transfer resistance of the electrode, and thereby affects the electrode reaction rate. The activity of species is also closely related to their concentration in the solution. Both SO 4 and H þ concentration in the anolyte increased during electrolysis, and thereby improved the activity of both ions, while SO 2 kept at atmo- spheric pressure. Then h a increased during electrolysis. I 2 concentration in the catholyte decreased, while I

2

Table 1 e Operating conditions tested for the electrochemical Bunsen reaction.

 

Run Current Temperature

Conc.

Conc.

I

2 /HI

 

density (A/dm 2 )

(K)

H

2 SO 4

HI ðmol =kg H 2 O Þ

molar

ðmol=kg H 2 O Þ

ratio

1

1

303

10

6

0.5

2

2.5

3

3.5

4

5

5

15

6

25

7

5

323

10

6

0.5

8

343

9

5

303

13

6

0.5

10

16

11

5

303

10

7

0.5

12

8

13

5

303

10

6

0.2

14

0.8

concentration increased with the electrolysis, so h c (less than 0) diminished during electrolysis, but its absolute value amplified. Therefore, the charge transfer resistance of both anode and cathode increased with the proceeding of electro- chemical reactions, so the reaction rate steadily decreased. However, since more H þ was produced at anode, the con- centration difference between two compartments was enlarged, thus the transport rate of H þ was increased, and more H þ could migrate from anode compartment to the cathode. According to the above analyses, the electrode re- action and the transport of H þ tend to be equilibrium with the electrolysis.

3.2.

Concentration of H 2 SO 4 and HI solution

3.2.1.

Effect of current density

Fig. 3 shows the variation of anolyte and catholyte concen- tration during electrolysis at different current densities. The symbols in the figure indicate the average of three measure- ments conducted at each condition, and the error bars show the calculated standard deviation, which remain less than

1.5%.

For most current densities, the H 2 SO 4 concentration in the anolyte augmented in the course of electrolysis ( Fig. 3 a). For a

current density of 1 A/dm 2 , the H 2 SO 4 molality amplified to a

maximum value of 5.147 mol/kg before declining at the last hour. This can be attributed to rise in cell resistance, and the electrode reaction of SO 2 became slower at low current den- sity. However, the total weight of anolyte increased, along with the dissolution of SO 2 , leading to a decrease in H 2 SO 4 molality. When the current density rose to 2.5 e3.5 A/dm 2 , the molality of H 2 SO 4 amplified at 1 h and then diminished before rising again at 3e4 h. The cell resistance was low and the

electrode reaction was fast at the start of electrolysis, with a large quantity of H þ generated at the anode, but the transport of H þ from anode to cathode was slower than the anode re- action; hence, at the first hour the molality of H þ was higher than that of SO 4 . During electrolysis more H þ moves from the anolyte to the catholyte while the electrode reaction became slower; then, at 2 h the H 2 SO 4 concentration declined. How- ever, as the anode reaction and H þ migration tended to equilibrium with the electrolysis, leading to rising H 2 SO 4 concentration again at 3 e4 h. When the current density increased to values above 5 A/dm 2 , the H 2 SO 4 molality

increased steadily during electrolysis, indicating the equilib-

rium between the electrode reaction and the transport of H þ . However, for the current density higher than 15 A/dm 2 , the anode-side graphite electrode could react with H 2 O into CO 2 or CO over 3 V of the cell voltage [11]; some carbon scraps were found in the anolyte, which affected the H 2 SO 4 concentration. At 25 A/dm 2 of the current density, the electrolysis was per- formed only 3 h according to the theoretical calculation that the completion of reaction was no more than 3 h, so only three points were obtained. The HI concentration in the catholyte increased with the electrolysis, and increase in current density increased HI concentration, as shown in Fig. 3 b. At the first hour of reac- tion, the measured molality of H þ in catholyte was lower than that of I , which was mainly due to the fact that the cathode reaction rate was higher than the proton transport rate,

2

6.4 (a) 1 A/dm 2 6.2 2.5 A/dm 2 3.5 A/dm 2 6.0 5 A/dm
6.4
(a)
1
A/dm 2
6.2
2.5
A/dm 2
3.5
A/dm 2
6.0
5
A/dm 2
2
15
A/dm
5.8
2
25
A/dm
5.6
5.4
5.2
5.0
H 2 SO 4 molality (mol/kg)
1.0 1.5 2.0 2.5 3.0 3.5 4.0 Electrolytic time (h) 0.85 (c) 1 A/dm 2
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Electrolytic time (h)
0.85
(c)
1
A/dm 2
0.80
2.5
A/dm 2
3.5
A/dm 2
0.75
5
A/dm 2
2
15
A/dm
0.70
2
25
A/dm
0.65
0.60
0.55
0.50
0.45
1.0
1.5
2.0
2.5
3.0
3.5
4.0
I 2 molality (mol/kg)

Electrolytic time (h)

3.6 (b) 1 A/dm 2 3.4 2.5 A/dm 2 3.5 A/dm 2 5 A/dm 2
3.6
(b)
1
A/dm 2
3.4
2.5
A/dm 2
3.5
A/dm 2
5
A/dm 2
3.2
2
15
A/dm
2
25
A/dm
3.0
2.8
2.6
1.0
1.5
2.0
2.5
3.0
3.5
4.0
HI molality (mol/kg)

Electrolytic time (h)

Fig. 3 e Evolution of anolyte and catholyte concentration during electrolysis at different current densities. (a) H 2 SO 4 concentration in anolyte, (b) HI concentration in catholyte, (c) I 2 concentration in catholyte (Anolyte: H 2 SO 4 [ 10 mol=kg H 2 O , Catholyte: HI [ 6 mol= kg H 2 O and I 2 /HI [ 0.5, T [ 303 K).

therefore, the HI concentration at 1 h depended on H þ molality. Then, more H þ migrated from anode to cathode compartment during electrolysis along with the permeation of H 2 O, SO 4 , and SO 2 driven by electroosmotic flow, besides, rising charge transfer resistance resulted in the slowdown of electrode reaction, as a result, the measured H þ molality was higher than I molality, I molality determined the concen- tration of HI. For the current density lower than 2.5 A/dm 2 , the HI concentration increased at the first hour because the cathode reaction was fast, then the cathode reaction slowed down and the catholyte weight increased with the permeation of hydronium ions, leading to the decrease of HI molality at 2 h. At the last two hours, HI concentration increased again because the equilibrium was reached between electrode re- action and proton transport. For current density above 3.5 A/ dm 2 , the HI concentration steadily increased during electrol- ysis, which suggested that increase in current density might favor the match between proton transport and cathode reaction. As seen in Fig. 3c, the I 2 concentration decreased during the first 3 h and then increased at 4 h. This might be due to the occurrence of side reactions at cathode, permeated SO 4 and SO 2 reacted with HI in the catholyte. At low current density, white particles were found to deposit on the membrane and cathode, which was also found by Nomura

2

2

et al. [11], indicating the formation of sulfur, two reactions might occurred at cathode compartment: H 2 SO 4 þ 6HI / S þ 3I 2 þ 4H 2 O, SO 2 þ 4HI / S þ 2I 2 þ 2H 2 O. At higher current density, H 2 S was detected, the chemical re- actions might be H 2 SO 4 þ 8HI / H 2 S þ 4I 2 þ 4H 2 O, and/or SO 2 þ 6HI / H 2 S þ 3I 2 þ 2H 2 O. Increase in current density contributed to rising H 2 SO 4 and HI concentration in anolyte and catholyte, respectively. However, a higher current density caused the corrosion of anode-side carbon electrode and increased the consumption of electric energy. In view of this, effects of other operating parameters were studied at current density of 5 A/dm 2 .

3.2.2. Effect of temperature

Fig. 4 shows the evolution of anolyte and catholyte concen- tration at different temperatures. As seen in Fig. 4a, at each temperature H 2 SO 4 was concentrated during electrolysis. The molality of H 2 SO 4 decreased for rising temperature from 303 K to 323 K and then increased from 323 K to 343 K. This trend might be due to two factors [16]. The first one is that an in- crease in temperature decreases the solubility of SO 2 , so that

the conversion of SO 2 to H 2 SO 4 diminished when the tem- perature increased to 323 K, the final H 2 SO 4 molality decreased from 5.455 mol/kg at 303 K to 5.356 mol/kg at 323 K. The sec- ond one is that electrode reaction rates increase with rising

5.60 (a) 303 K 5.55 323 K 343 K 5.50 5.45 5.40 5.35 5.30 5.25
5.60
(a)
303
K
5.55
323
K
343
K
5.50
5.45
5.40
5.35
5.30
5.25
5.20
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Electrolytic time (h)
1.2
(c)
303
K
1.1
323
K
343
K
1.0
0.9
0.8
0.7
0.6
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
H 2 SO 4 molality (mol/kg)
I 2 molality (mol/kg)
HI molality (mol/kg)

Electrolytic time (h)

3.3

3.2

3.1

3.0

2.9

2.8

2.7

2.6

(b) 303 K 323 K 343 K 1.0 1.5 2.0 2.5 3.0 3.5 4.0
(b)
303
K
323
K
343
K
1.0
1.5
2.0
2.5
3.0
3.5
4.0

Electrolytic time (h)

Fig. 4 e Evolution of anolyte and catholyte concentration during electrolysis at different temperatures. (a) H 2 SO 4 concentration in anolyte, (b) HI concentration in catholyte, (c) I 2 concentration in catholyte (Anolyte: H 2 SO 4 [ 10 mol =kg H 2 O , Catholyte: HI [ 6 mol=kg H 2 O and I 2 /HI [ 0.5, Current density [ 5 A/dm 2 ).

temperature, and the activities of solutions are higher at higher temperatures, as a result, the final H 2 SO 4 concentration increased again to 5.530 mol/kg at 343 K. The evolution of the HI concentration at different temper- atures is shown in Fig. 4b. At 303 K, the HI molality increased steadily from 2.750 mol/kg to 3.066 mol/kg during electrolysis. For the temperature of 323 K and 343 K, HI molality increased to a high value at the first hour, which was due to the high elec- trode reactions rates. Then the molality of HI decreased to a minimum value at 2 h before increasing again at the last two hours. This can be attributed to the decrease of cathode reac- tion rate and increase of proton transport rate. The molality of HI increased for rising temperature from 303 K to 323 K and then decreased for the further increase of temperature to 343 K. The highest HI concentration of 3.193 mol/kg was obtained at 323 K after 4 h electrolysis. As shown in Fig. 4c, increase in temperature increased I 2 concentration in catholyte. Though the activity of I 2 was improved at higher temperature, rising temperature inhibited the conversion of I 2 , leading to rising I 2 concentration.

3.2.3. Effect of H 2 SO 4 concentration

Fig. 5 shows the evolution of anolyte and catholyte concen- tration for three initial H 2 SO 4 concentrations of 10, 13, and

16 mol=kg H 2 O in anolyte. Increase in the initial H 2 SO 4 con-

centration reduced the solubility of SO 2 , then the change in concentrations of both the H 2 SO 4 and the dissolved SO 2 affected the activity of anolyte. The performance of the entire electrochemical cell, including the cathode reaction, was

influenced as well. Fig. 5a shows that the H 2 SO 4 molality drastically increased at the first hour and then changed slowly with the electrolysis, which suggested that the anode reaction was fast at the beginning of the electrolysis and then slowed down. Increasing the initial H 2 SO 4 concentration amplified

the H 2 SO 4 molality and the difference between H 2 SO 4 molality at the same time was comparable. As shown in Fig. 5b and c, the finial HI molality increased from 3.066 mol/kg to 3.243 mol/ kg for rising H 2 SO 4 concentration from 10 mol=kg H 2 O to

13 mol= kg H 2 O , but then slightly lessened with further increase

of H 2 SO 4 concentration to 16 mol=kg H 2 O . On the contrary, I 2

molality declined as the concentration of H 2 SO 4 rose from

10 mol=kg H 2 O to 13 mol=kg H 2 O and then amplified as the H 2 SO 4

concentration increased to 16 mol=kg H 2 O . The cell resistance

might be the lowest and the conversion of reactants was highest at 13 mol=kg H 2 O of H 2 SO 4 concentration. At higher H 2 SO 4 concentration, the membrane tended to dehydrate and its conductivity decreased. Therefore, a H 2 SO 4 concentration of 13 mol =kg H 2 O might be an optimal choice.

6.75 (a) 6.50 6.25 6.00 5.75 5.50 5.25 H 2 SO 4 concentration 5.00 10
6.75
(a)
6.50
6.25
6.00
5.75
5.50
5.25
H 2 SO 4 concentration
5.00
10
mol/kg
H2O
13
mol/kg
H2O
4.75
16
mol/kg
H2O
4.50
H 2 SO 4 molality (mol/kg)
HI molality (mol/kg)

3.3

3.2

3.1

3.0

2.9

2.8

2.7

H 2 SO 4 concentration (b) 10 mol/kg H2O 13 mol/kg H2O 16 mol/kg H2O
H 2 SO 4 concentration
(b)
10
mol/kg
H2O
13
mol/kg
H2O
16
mol/kg
H2O

01234 1.0

1.5

2.0

2.5

3.0

3.5

4.0

Electrolytic time (h)

Electrolytic time (h)

0.8 (c) H 2 SO 4 concentration 10 mol/kg H2O 13 mol/kg H2O 0.7 16
0.8
(c)
H 2 SO 4 concentration
10
mol/kg
H2O
13
mol/kg
H2O
0.7
16
mol/kg
H2O
0.6
0.5
0.4
1.0
1.5
2.0
2.5
3.0
3.5
4.0
I 2 molality (mol/kg)

Electrolytic time (h)

Fig. 5 e Evolution of anolyte and catholyte concentration during electrolysis for different H 2 SO 4 concentrations. (a) H 2 SO 4 concentration in anolyte, (b) HI concentration in catholyte, (c) I 2 concentration in catholyte (Catholyte: HI [ 6 mol=kg H 2 O and I 2 /HI [ 0.5, T [ 303 K, Current density [ 5 A/dm 2 ).

3.2.4. Effect of HI concentration

Fig. 6 shows the variation of anolyte and catholyte concen- tration for three different initial HI concentrations in cath- olyte (6, 7, 8 mol=kg H 2 O ). The I 2 concentration was also altered, to keep the I 2 /HI molar ratio at 0.5. Rising initial HI concentration improved the activities of the catholyte and thereby increased the cathode reactions rates. Meanwhile, the anode reaction could be affected as well. As shown in Fig. 6a and b, the molality of both H 2 SO 4 and HI enlarged as the initial HI concentration rose from 6 mol=kg H 2 O to 7 mol =kg H 2 O . However, when the initial HI concentration further increased to 8 mol=kg H 2 O , the HI molality continued growing because of the high initial concentration, while the H 2 SO 4 molality diminished, which may be due to rising cell resistance and a reduction of anode reaction rate. The vari- ations of both the HI molality and the I 2 molality were sig- nificant at the first hour and then became slow at the last 3 h. The I 2 molality declined during electrolysis, and it increased with rising initial HI concentration since the initial I 2 con- centration was increased as well. But the side reactions occurred at 4 h for the initial HI concentration of 6 mol=kg H 2 O contributed to the increase of I 2 molality, so the lowest I 2 molality of 0.634 mol/kg was obtained at initial HI concen- tration of 7 mol=kg H 2 O . Then, a HI concentration of

7 mol=kg H 2 O was advantageous as far as the final solution concentration was concerned.

3.2.5. Effect of I 2 /HI molar ratio

Fig. 7 shows the variation of solution concentration for three different I 2 /HI molar ratios in catholyte (0.2, 0.5, 0.8). A rise in I 2 /HI molar ratio amplified the I 2 concentration and therefore improved the activity of I 2 in the catholyte; then the overpotential at the cathode for reduction of I 2 to I was reduced, but the resistance of catholyte solution could in- crease [13] . As shown in Fig. 7a, the H 2 SO 4 molality rose with increasing I 2 /HI ratio, which might be due to the improvement in electrode kinetics and the slowdown of proton permeation at higher I 2 concentration. In Fig. 7b, the HI molality contin- uously increased during electrolysis, and it was higher at the lower I 2 /HI molar ratio because of the corresponding higher initial HI concentration. Increase in I 2 /HI molar ratio amplified the total weight of catholyte and thereby reduced the initial HI concentration. For an I 2 /HI molar ratio of 0.5 and 0.8, the I 2 molality increased at the last hour, possibly related to the occurrence of side reactions in the catholyte, since white particles were found to deposit on the membrane and cath- ode. For the traditional direct contact mode of Bunsen

5.8 3.3 HI concentration (a) 3.2 6 mol/kg H2O 5.7 7 mol/kg 3.1 H2O 8
5.8
3.3
HI concentration
(a)
3.2
6 mol/kg
H2O
5.7
7 mol/kg
3.1
H2O
8 mol/kg
H2O
3.0
5.6
2.9
5.5
2.8
2.7
5.4
2.6
2.5
5.3
2.4
5.2
2.3
1.0
1.5
2.0
2.5
3.0
3.5
4.0
H 2 SO 4 molality (mol/kg)
HI molality (mol/kg)

Electrolytic time (h)

1.4 (c) HI concentration 6 mol/kg H2O 1.2 7 mol/kg H2O 8 mol/kg H2O 1.0
1.4
(c)
HI concentration
6 mol/kg
H2O
1.2
7 mol/kg
H2O
8 mol/kg
H2O
1.0
0.8
0.6
I 2 molality (mol/kg)

01234

Electrolytic time (h)

(b) HI concentration 6 mol/kg H2O 7 mol/kg H2O 8 mol/kg H2O
(b)
HI concentration
6 mol/kg
H2O
7 mol/kg
H2O
8 mol/kg
H2O

01234

Electrolytic time (h)

Fig. 6 e Evolution of anolyte and catholyte concentration during electrolysis for different HI concentrations. (a) H 2 SO 4 concentration in anolyte, (b) HI concentration in catholyte, (c) I 2 concentration in catholyte (Anolyte: H 2 SO 4 [ 10 mol =kg H 2 O , Catholyte: I 2 /HI [ 0.5, T [ 303 K, Current density [ 5 A/dm 2 ).

reaction, the optimal I 2 /HI value is in the range of 2 e3 [18] . However, in the electrochemical Bunsen reaction, two acids with high purity can be obtained with a lower excess amount of iodine.

3.3. Proton transport and water permeability

In the electrochemical cell the transport properties of the cation exchange membrane can be characterized by two pa- rameters: the transport number of proton ( t þ ) and the water permeability coefficient ( b) [19e21]. These parameters are defined as follows:

c

HI

t þ ¼ FD N It

(11)

b ¼

D N c

H 2 O

D

N c

HI

(12)

Here, DN HI and DN H 2 O are the molar change of HI and of H 2 O in catholyte (mol). I , t, and F respectively denote the electric current (A), the electrolytic time (s), and the Faraday constant (96,485 C/mol). At each operating condition, the weight of anolyte and catholyte were measured after electrolysis by collecting the solution from the glass reservoirs. Small

c

c

amounts of solutions remained in the cell and tubes, however, which caused some errors in weighting the solutions. The parameters t þ and b obtained designate the entire process of the electrochemical Bunsen reaction. Table 2 lists the t þ and b values for different runs; Q e denotes the total amount of electricity consumed during electrolysis (C). In runs 1 e4, values of t þ close to 1 indicate that the transport of H þ was flawless whenever the current density remained below 5 A/dm 2 . However, the value of t þ decreased to less than 0.5 as current density further amplified to 15 and 25 A/dm 2 . The variation of b was con- trary to t þ , an increase in current density decreasing the permeation of water. For runs 7 e14, t þ was higher than 0.95, which indicated that the proton transport rate was high and that the HI in catholyte was fully concentrated. When the temperature increased from 303 K to 323 K and to 343 K, t þ increased while b drastically decreased to less than 0.15, indicating rising temperature promoted the concentration of HI in catholyte, which was in agreement with the result in Section 3.2.2 . The parameter t þ increased while b first increased and then decreased with rising H 2 SO 4 concen- tration in anolyte and HI concentration in catholyte. An increase in the I 2 /HI molar ratio increased the permeation of water into cathode compartment.

5.7 I 2 /HI (a) (a) 0.2 5.6 0.5 0.8 5.5 5.4 5.3 5.2 1.0
5.7
I
2 /HI
(a)
(a) 0.2
5.6
0.5
0.8
5.5
5.4
5.3
5.2
1.0
1.5
2.0
2.5
3.0
3.5
4.0
H 2 SO 4 molality (mol/kg)
HI molality (mol/kg)

Electrolytic time (h)

1.6 I 2 /HI (c) 0.2 0.5 0.8 1.2 0.8 0.4 0.0 I 2 molality
1.6
I
2 /HI
(c)
0.2
0.5
0.8
1.2
0.8
0.4
0.0
I 2 molality (mol/kg)

01234

Electrolytic time (h)

4.0

(b)

I 2 /HI 0.2 0.5 0.8
I
2 /HI
0.2
0.5
0.8
 

3.6

 
3.6  
3.6  
   
   

3.2

 
 
 
 
 

2.8

2.8  
 
2.8  
 
   
 
   

2.4

2.4  
2.4  
2.4  
 
   

2.0

2.0

01234

Electrolytic time (h)

Fig. 7 e Evolution of anolyte and catholyte concentration during electrolysis for different I 2 /HI molar ratios. (a) H 2 SO 4 concentration in anolyte, (b) HI concentration in catholyte, (c) I 2 concentration in catholyte (Anolyte: H 2 SO 4 [ 10 mol=kg H 2 O , Catholyte: HI [ 6 mol= kg H 2 O , T [ 303 K, Current density [ 5 A/dm 2 ).

3.4. Evaluation of current efficiency and energy

consumption

For each run, the current efficiency for both electrode re- actions was calculated by comparing the change in the amount of acids with the amount expected from the amount of charge supplied by the D.C. power [13]. It is defined as follows:

Anode h ¼

a

I

D

N

a

H 2 SO 4

It= 2F

(13)

Cathode h ¼

c

I

D

N

c

HI

It =F

(14)

Here, h and h denote the current efficiency of anode and cathode. DN H 2 SO 4 and DN HI are the measured molar increase of H 2 SO 4 in anolyte and HI in catholyte, respectively. It /2F and It/ F are the theoretical moles of H 2 SO 4 and HI formed during electrolysis, 2 indicates that two mole electrons are required per mole of H 2 SO 4 formed. I , t , and F denote the constant current (A), the electrolytic time (s), and the Faraday constant (96,485 C/mol). Since the final desired product of the SI cycle is H 2 , the energy consumed in the electrochemical cell should be re- ported in terms of hydrogen produced. Heat equivalent of

a

I

a

c

I

c

electric energy consumed per mole of H 2 at each run is calculated using Eq. (15) [16] .

U H 2 ¼ 2 FV e h E h

c

I

(15)

Here V e is the average cell voltage (V), which is calculated using the integral of the voltage with electrolytic time, and the obtained integral value is then divided by the total electrolytic time. F is the Faraday constant (96,485 C/mol), h E is the effi- ciency for conversion of heat to electricity, which is assumed 0.4, and h is the current efficiency of cathode. Table 3 shows the data for current efficiency of anode and cathode and heat equivalent of electric energy consumed per mole of H 2 after electrolysis. For current density of 1 A/dm 2 , h

was less than 50%, which was due to the decrease of H 2 SO 4 molality at the last hour ( Section 3.2.1). For the low current density of 2.5 e3.5 A/dm 2 , h was slightly above 100%. This may be explained by three factors: the first one is the uncertainties in sampling and titration, the second is that a small amount of residual SO 2 remained in anolyte and thereby interferes the titration of H þ , and the last one is that the electroosmosis flow from anode to cathode decreased the weight of anolyte and thus increased the concentration of H 2 SO 4 in anolyte [13]. When the current density further increased to 15 and 25 A/

c

I

a

I

a

I

Table 2 e t D and b at different operating conditions.

Run

Q e (C)

t þ

b

1 1728

0.928

7.751

2 4464

0.985

6.866

3 6192

0.925

4.743

4 8784

0.926

2.696

5 26496

0.379

2.579

6 33048

0.462

1.658

7 8784

0.999

0.146

8 8784

0.953

0.025

9 8784

0.990

4.861

10 8784

1.002

1.805

11 8784

0.985

5.322

12 8784

1.002

4.704

13 8784

0.959

0.629

14 8784

0.954

5.292

dm 2 , h and h drastically decreased to less than 80%. For the

I a and h reached the

temperature of 303, 323, and 343 K, h

maximum value at 343 K and 323 K, respectively, agreeing well with the results in Section 3.2.2. Increase in H 2 SO 4 concen- tration in anolyte or HI concentration in catholyte increased the current efficiency of anode and cathode. Value of electrode current efficiency close to 100% for Run 9e 12 suggested that no side reactions occurred and there were no homogeneous

reactions between the reactants that could lead to change in the concentration of H 2 SO 4 and HI [13]. Therefore, a higher initial H 2 SO 4 and HI concentration were preferred for anolyte and catholyte to suppress the side reaction of sulfur and

c I first

decreased and then increased as the I 2 /HI molar ratio rose from 0.2 to 0.8. As shown in Table 3 , the lowest U H 2 of 108.92 kJ/mol-H 2 was obtained at current density of 1 A/dm 2 , while value of U H 2 at 15 and 25 A/dm 2 were much higher. A lower U H 2 can be obtained at lower current densities and will lead to a higher thermal efficiency of SI cycle. However, the H 2 production rate may be reduced at a lower current density, then the required size of electrochemical cell and membrane area must increase for a given production rate, leading to rising capital cost [14] .

hydrogen sulfide formation. h

a

I

c

I

c

I

I a increased while h

Table 3 e Current efficiency and energy consumption at different operating conditions.

Run

h (%)

a

I

h (%)

c

I

V e (V)

U H 2 (kJ/mol-H 2 )

1 42.46

92.77

0.21

108.92

2 100.09

98.51

0.33

161.10

3 100.08

92.50

0.46

237.93

4 95.25

92.60

1.67

869.07

5 67.41

37.88

3.46

4412.60

6 76.04

46.25

3.69

3849.30

7 90.09

99.86

1.08

523.04

8 98.29

95.32

0.93

468.32

9 99.84

99.03

1.55

756.51

10 99.98

100.25

1.45

699.16

11 100.11

98.45

0.56

276.84

12 100.06

100.22

0.82

393.24

13 93.61

95.90

0.48

240.07

14 98.92

95.41

0.56

281.68

Increase in temperature increased the activity of anolyte and catholyte and thereby increased electrode reaction rates, the cell resistance was reduced and V e decreased, leading to the decrease of U H 2 . V e slightly decreased with rising H 2 SO 4 con- centration, and the reduction of U H 2 was also small. Increase in HI concentration increased the activity of catholyte and decreased the cell resistance, as a result, both V e and U H 2 diminished significantly. I 2 /HI molar ratio has two effects on cell voltage [13]. An increase in I 2 /HI molar ratio increases I 2 concentration and therefore reduces the required over- potential at cathode for reduction of I 2 to I . On the other hand, increase in I 2 concentration also increases ohmic resistance of the catholyte and hence increases the cell voltage. As I 2 /HI ratio increased from 0.2 to 0.5, the ohmic voltage drop may be the major effect, thus V e increased. But the voltage decreased with further increase of I 2 /HI molar ratio to 0.8, which was due to the reduction of overpotential at cathode was more than the increase in ohmic voltage drop. As

the I 2 /HI molar ratio increased from 0.2 to 0.8, U H 2 increased

from 240.07 kJ/mol-H 2 to 869.07 kJ/mol-H 2 and then decreased to 281.68 kJ/mol-H 2 , which was in accordance with the varia- tion of voltage.

4.

Conclusions

The Bunsen reaction was successfully carried out using an electrochemical cell featuring a Nafion 117 membrane and

two graphite electrodes. Both H 2 SO 4 in the anolyte and HI in

the catholyte were concentrated during electrolysis. Increase in the current density contributed to elevating the H 2 SO 4 and HI concentration. However, a higher current density also caused corrosion of the anode-side graphite electrode and increased power consumption. As temperature increased from 303 K to 343 K, the highest H 2 SO 4 in anolyte and HI molality in catholyte were respectively obtained at 343 K and 323 K. The H 2 SO 4 molality in anolyte increased with rising initial H 2 SO 4 concentration while the HI molality in catholyte reached its highest value at 13 mol=kg H 2 O of H 2 SO 4 concen- tration. As the initial HI concentration amplified, the HI molality in catholyte increased while the H 2 SO 4 molality in anolyte first increased and then decreased. The H 2 SO 4 con- centration increased with rising I 2 /HI molar ratio, whereas a higher HI concentration can be obtained at a lower I 2 /HI molar ratio. Compared with the traditional Bunsen reaction, the electrochemical method generated two acids with high purity even at low excess iodine values. The value of t þ was close to 1 for most runs except at higher current densities, but an increase in current density reduced the permeation of water ( b). The electrode current efficiency drastically decreased to less than 80% as the current density augmented to 15 and 25 A/dm 2 , while the electrode current efficiency was close to 100% at other conditions. A lower U H 2 can be obtained at lower current densities, and the lowest U H 2 of 108.92 kJ/mol-H 2 was obtained at a current density of 1 A/ dm 2 . An increase in temperature, H 2 SO 4 concentration, and HI concentration lessened the value of U H 2 . But U H 2 increased as the I 2 /HI molar ratio increased from 0.2 to 0.5 and then decreased for further rises of I 2 /HI to 0.8.

Acknowledgments

This work has been financially supported by the National Natural Science Foundation of China (51276170). The authors gratefully acknowledge this support.

Nomenclature

E 0, j

Standard j -electrode potential (vs. standard hydrogen electrode (SHE)), V

DN

I

t

F

n

E j

a

p

i

SO

0

theoretical moles of i-component formed during

electric current, A

i

electrolysis, mol

electrolytic time, s

Faraday constant, 96,485 C/mol

2

number of electrons required in the half cell reaction, dimensionless j -electrode potential, V activity of i -species in the solution, dimensionless relative pressure of SO 2 in the anolyte, dimensionless

R gas constant, 8.31 J mol 1 K 1

T

h j

t þ

b water permeability coefficient, dimensionless

DN j

Q e

i

temperature, K j -electrode overpotential, V transport number of proton, dimensionless

molar change of i -component in j -electrolyte, mol total amount of electricity, C current efficiency of j -electrode, dimensionless heat equivalent of electric energy consumed per mole of H 2 , kJ/mol-H 2 average cell voltage, V efficiency for conversion of heat to electricity, dimensionless

h I j

U

H 2

V

h E

e

references

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